Ultrastable porous aluminosilicate structures and compositions derived therefrom

ABSTRACT

Porous hexagonal, cubic, lamellar, wormhole, or cellular foam aluminosilicates, gallosilicates and titanosilicates derived from protozeolitic seeds or zeolite fragments using an organic porogen directing agent are described. The porous aluminosilicates optionally also can contain zeolite crystals depending upon the aging of the protozeolitic seeds. The silicon and aluminum, gallium or titanium centers in the structures are stable so that the framework of the structure does not collapse when heated in the presence of water or water vapor (steam). The steam stable compositions can be used as catalysts for hydrocarbon conversions, including the fluidized bed catalytic cracking and the hydrocracking of petroleum oils, and other reactions of organic compounds.

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application is a continuation-in-part of Ser. No.09/578,315, filed May 25, 2000 and a continuation-in-part of Ser. No.09/792,017, filed Feb. 21, 2001.

STATEMENT REGARDING FEDERALLY FUNDED RESEARCH AND DEVELOPMENT

[0002] This invention was developed under National Science FoundationGrant Nos. CHE-9633798 and CHE-9903706. The U.S. government has certainrights to this invention.

BACKGROUND OF THE INVENTION

[0003] (1) Field of the Invention

[0004] The present invention relates to porous aluminosilicatecompositions which have a unique structure which are stable at hightemperatures and under hydrothermal conditions. In particular, thepresent invention relates to a process for producing the porousaluminosilicate composition which uses a zeolite seed or a zeolitefragment with a structure directing agent, referred to as an organicporogen. The porous aluminosilicate structures are mesoporous andoptionally can contain zeolite crystals, depending upon the aging of thezeolite seeds and the extent to which the zeolite fragments aredisordered. Further still, the present invention relates to novelcracking catalysts for oil and other organic molecules. The presentinvention thus provides for the assembly of ultrastable porousaluminosilicates with hexagonal, cubic, wormhole or foam frameworkstructures that do not suffer from the undesirable extensivede-alumination and steam instability of conventional aluminosilicatecompositions.

[0005] (2) Description of Related Art

[0006] All previously reported aluminosilicate mesostructures, asprepared by either direct or post synthesis alumination, result in theextensive de-alumination of the framework upon calcination (Ryoo, R., etal., Chem. Commun. 2225 (1997); and Luan, Z. H., et al., J. Phys. Chem.99 10590 (1995)). This undesired property has been attributed to thehydrolysis of the framework Al by steam generated in the calcinationprocess (Corma, A., et al., J. Catal. 148 569 (1994); and Luan, Z. H.,et al., J. Phys. Chem. 99 10590 (1995)). Regardless of the mechanismresponsible for the de-alumination process, the acid catalyticproperties of these materials for organic chemical conversions isgreatly compromised. Moreover, all previously reported aluminosilicatemesostructures completely lose their framework mesoporosity when exposedto steam at the temperatures normally encountered in the processing ofpetroleum catalysts.

[0007] Soon after the discovery of mesoporous MCM-41 molecular sieves(Beck, J. S., et al., J. Am. Chem. Soc. 114 10834 (1992)), it was foundthat the incorporation of aluminum into the framework introduced mildacidic functionality, but the long range order and tetrahedral siting ofthe aluminum was compromised (Chen, C-Y., et al., Microporous Mater. 217 (1993); Borade, R. B., et al., Catal. Lett 31 267 (1994); Luan, Z.H., et al., J. Phys. Chem. 99 10590 (1995)), especially at intendedaluminum loadings above about 8 mol %. Mild acidity and loss ofstructural integrity, together with poor steam stability underregeneration conditions made hexagonal Al-MCM-41 compositionsunattractive candidates for the processing of high molecular weightpetroleum fractions. More recently, important advances have been made inimproving the structural integrity of Al-MCM-41 through direct assembly(Janicke, M. T., et al., Chem. Mater. 11 1342 (1999)) and post synthesismodification methods (Hamdan, H., et al., J. Chem. Soc. Faraday Trans 922311 (1996); Mokaya, R., et al., Chem. Commun. 2185 (1997); Ryoo, R., etal., J. Chem. Commun. 2225 (1997); and Ryoo, R., et al., Chem. Mater. 91607 (1998)). However, the low acidity and poor steam stability stilllimit potential applications in petroleum refining (Corma, A., Chem.Rev. 2373 (1997)).

[0008] U.S. Pat. No. 5,264,203 to Beck et al describes mesoporousaluminosilicate compositions. The compositions are similar to thepresent invention but are not based upon pore forming zeolitic seeds orfragments thereof.

[0009] There is thus a need for improved aluminosilicate compositions,both mesostructured with larger pore sizes that are stable, particularlyin the presence of steam. In particular, the present invention relatesto aluminosilicates that have stable framework structures.

SUMMARY OF THE INVENTION

[0010] The present invention relates to a porous structuredaluminosilicate composition which comprises:

[0011] a framework of linked tetrahedral SiO₄ and AlO₄ units, theframework defining pores and having an Si to Al molar ratio of betweenabout 1000 to 1 and 1 to 1, and wherein the composition retains at least50% of an initial framework pore volume after exposure to 20 volume %steam at 800° C. for two hours.

[0012] The present invention also relates to a porous structuredaluminosilicate composition which comprises:

[0013] a framework of linked SiO₄ and AlO₄ units, the framework definingpores and having a Si to Al molar ratio of about 1000 to 1 and 1 to 1,and having at least one X-ray diffraction peak between 2 and 100 nm, andwherein the composition retains at least 75% of an initial frameworkpore volume after exposure to 20 volume percent steam at 600° C. forfour hours.

[0014] The present invention also relates to a porous structuredaluminosilicate composition which comprises:

[0015] a framework of linked tetrahedral SiO₄ and AlO₄ units, theframework defining pores having an organic surfactant in the pores andhaving a Si to Al molar ratio of between 1000 to 1 and 1 to 1 and havingat least one X-ray diffraction peak corresponding to a basal spacingbetween about 2 and 100 nm and wherein the composition is derived from aporogen and preformed zeolite seeds or zeolite fragments.

[0016] The present invention also relates to a process for forming aporous aluminosilicate composition which comprises:

[0017] (a) providing zeolite seeds or zeolite fragments in a formselected from the group consisting of an aqueous solution, gel,suspension wetted powder and mixtures thereof;

[0018] (b) mixing in a mixture the zeolite seeds or zeolite fragments inan aqueous medium with an organic porogen;

[0019] (c) aging the mixture of step (b) at a temperature between 25°and 200° C. to obtain a precipitate of the composition; and

[0020] (d) separating the composition from the mixture of step (c).

[0021] The present invention further relates to a structuredaluminosilicate porous composition which comprises:

[0022] a framework of linked tetrahedral SiO₄ and AlO₄ units, theframework defining mesopores, having a porogen or a surfactant, aporogen in the pores of the composition having an Si to Al molar ratioof between about 1000 to 1 and 1 to 1, and having at least one X-raydiffraction peak corresponding to a basal spacing between about 2.0 and100 nm, and which when calcined retains at least 50% of an initialframework pore volume after exposure to 20 volume % steam at 800° C. fortwo hours.

[0023] The present invention also relates to a porous aluminosilicatecomposition which comprises: a framework of tetrahedral linked SiO₄ andAlO₄ units, the framework defining mesopores having an Si to Al molarratio of between about 1000 to 1 and 1 to 1, and having at least oneX-ray diffraction peak corresponding to a basal spacing between about2.0 and 100 nm, wherein a BET surface area is between 200 and 1400 m²per gram, wherein an average pore size of the framework is between about1.0 and 100 nm, and wherein a pore volume of the framework is betweenabout 0.1 and 3.5 cm³ per gram, and which retains at least 50% of aninitial framework pore volume after exposure to 20 volume % steam at800° C. for two hours.

[0024] The present invention further relates to a hybrid porousaluminosilicate-carbon composition which comprises: a framework oflinked tetrahedral SiO₄ and AlO₄ units, the framework defining mesoporeshaving an Si to Al molar ratio of between about 1000 to 1 and 1 to 1 andbetween 0.01 and 50 wt % carbon embedded in the mesopores, and having atleast one X-ray diffraction peak corresponding to a basal spacingbetween about 2.0 and 100 nm, wherein a BET surface area is between 100and 1400 m² per gram, wherein an average pore size of the framework isbetween about 1.0 and 100 nm, and wherein a pore volume of the frameworkis between about 0.1 and 3.5 cm³ per gram, and which retains at least50% of an initial framework pore volume after exposure to 20 volume %steam at 800° C. for two hours.

[0025] The present invention further relates to a composition preparedby treating the composition of claim 20 before calcining with anammonium salt solution at a temperature between about 0° and 200° C. fora period of up to 24 hours and repeating the treatment up to ten timesto introduce ammonium ions into the composition, collecting and dryingthe resulting composition, and then calcining the resulting compositionat a temperature between about 40° and 900° C. to remove the organicporogen and to convert a fraction of the surfactant or other organicporogen to carbon embedded in the mesopores.

[0026] The present invention further relates to a process for forming aporous aluminosilicate composition which comprises:

[0027] (a) reacting a sodium silicate solution at basic pH with a sodiumaluminate solution at an aluminum to silicon ratio between about 1000 to1 and 1 to 1 and aging the mixture at 25 to 200° C. for periods of up to48 hours to form zeolite seeds;

[0028] (b) mixing the resultant mixture with an organic porogen;

[0029] (c) reducing a pH of the mixture obtained from (b) with aprotonic acid to obtain a mixture with an OH⁻/(Si+Al) ratio in the rangeof 0.10 to 10;

[0030] (d) aging the mixture from step (c) at a temperature between 20and 200° C. to obtain a precipitate of the composition; and

[0031] (e) separating the composition from mixture of step (d).

[0032] The present invention further relates to a process for forming aporous aluminosilicate composition which comprises:

[0033] (a) providing zeolite seeds or zeolite fragments in a formselected from the group consisting of an aqueous solution, gel,suspension, wet powder, or combination thereof;

[0034] (b) reacting the zeolite seeds in the aqueous medium with anorganic porogen wherein the solution has an OH⁻/(Si+Al) ratio in therange of 0.10 to 10;

[0035] (c) aging the mixture from step (b) at a temperature between 20and 200° C. to obtain a precipitate of the composition; and

[0036] (d) separating the composition from the mixture of step (c).

[0037] The present invention further relates to a catalyst useful for afluidized bed catalytic cracking (FCC) or hydrocracking of an organicmolecule which comprises:

[0038] (a) a porous aluminosilicate composition which comprises aframework of linked tetrahedral SiO₄ and AlO₄ units, the frameworkdefining mesopores having an Si to Al molar ratio of between about 1000to 1 and 1 to 1, wherein a BET surface area is between 200 and 1400 m²per gram, wherein an average pore size of the framework is between about1.0 and 100 nm, and wherein a pore volume of the framework is betweenabout 0.1 and 3.5 cm³ per gram, and which retains at least 50% of aninitial framework pore volume after exposure to 20 volume % steam at800° C. for two hours; and

[0039] (b) a binder for the aluminosilicate composition.

[0040] The present invention further relates to a catalyst useful forfluidized bed catalytic cracking (FCC) or hydrocracking of an organicmolecule which comprises:

[0041] (a) a porous aluminosilicate-carbon composition which comprises aframework of linked tetrahedral SiO₄ and AlO₄ units, the frameworkdefining mesopores having an Si to Al molar ratio of between about 1000to 1 and 1 to 1 and between 0.01 and 50 wt % carbon embedded in themesopores, and having at least one X-ray diffraction peak correspondingto a basal spacing between about 2.0 and 100 nm, wherein a BET surfacearea is between 100 and 1400 m² per gram, wherein an average pore sizeof the framework is between about 1.0 and 100 nm, and wherein a porevolume of the framework is between about 0.1 and 3.5 cm³ per gram,wherein the carbon content is between 0.01 and 50% by weight, and whichretains at least 50% of an initial framework pore volume after exposureto 20 volume % steam at 800° C. for two hours; and

[0042] (b) a binder for the aluminosilicate-carbon composition.

[0043] The present invention further relates to a process for catalyticreaction of an organic molecule into lower molecular weight components,which comprises:

[0044] (a) providing in a reactor a catalytic cracking catalyst whichcomprises: a porous aluminosilicate composition which comprises aframework of linked tetrahedral SiO₄ and AlO₄ units, the frameworkdefining mesopores having an Si to Al molar ratio of between about 1000to 1 and 1 to 1, wherein a BET surface area is between 200 and 1400 m²per gram, wherein an average pore size of the framework is between about1.0 and 100 nm, and wherein a pore volume of the framework is betweenabout 0.1 and 3.5 cm³ per gram; and a binder for the aluminosilicatecomposition, and which retains at least 50% of an initial framework porevolume after exposure to 20 volume % steam at 800° C. for two hours; and

[0045] (b) introducing the organic molecule onto the catalyst attemperatures and pressures which cause the reaction of the organicmolecule.

[0046] The present invention further relates to a process for reactionof an organic molecule into lower molecular weight components, whichcomprises:

[0047] (a) providing in a reactor a catalytic cracking catalyst whichcomprises: a porous aluminosilicate-carbon composition which comprises:a framework of tetrahedral linked SiO₄ and AlO₄ units, the frameworkdefining mesopores having an Si to Al molar ratio of between about 1000to 1 and 1 to 1 and between 0.01 and 50 wt % carbon embedded in themesopores, and having at least one X-ray diffraction peak correspondingto a basal spacing between about 2.0 and 100 nm, wherein a BET surfacearea is between 100 and 1400 m² per gram, wherein an average pore sizeof the framework is between about 1.0 and 100 nm, and wherein a porevolume of the framework is between about 0.1 and 3.5 cm³ per gram; and abinder for the aluminosilicate-carbon composition, and which retains atleast 50% of an initial framework pore volume after exposure to 20volume % steam at 800° C. for two hours; and

[0048] (b) introducing the organic molecule onto the catalyst attemperatures and pressures which cause the reaction of the organicmolecule into lower molecular weight components.

[0049] The present invention further relates to a catalyst useful for afluidized bed catalytic cracking (FCC) or hydrocracking of an organicmolecule which comprises:

[0050] (a) a porous structured aluminosilicate composition whichcomprises:

[0051] a framework of linked tetrahedral SiO₄ and AlO₄ units, theframework defining pores and having an Si to Al molar ratio of betweenabout 1000 to 1 and 1 to 1, and wherein the composition retains at least50% of the initial framework pore volume after exposure to 20 volume %steam at 800° C. for two hours; and

[0052] (b) a binder for the aluminosilicate composition. The structureshave at least one X-ray diffraction peak corresponding to a basalspacing between about 2.0 nm and 100 nm. Again these structures can haveno x-ray diffraction pattern if the pores are irregularly formed.

[0053] The present invention further relates to a process for reactionof an organic molecule into lower molecular weight components whichcomprises:

[0054] (a) providing a porous structured aluminosilicate compositionwhich comprises:

[0055] a framework of linked tetrahedral SiO₄ and AlO₄ units, theframework defining pores and having an Si to Al molar ratio of betweenabout 1000 to 1 and 1 to 1, and having at least one X-ray diffractionpeak corresponding to a basal spacing between about 1 and 100 nm, andwherein the composition retains 50% of the initial framework pore volumeupon exposure to 20 volume percent steam at 800° C. for two hours; and

[0056] (b) introducing the organic molecule onto the catalyst attemperatures and pressures which cause the reaction of the organicmolecule to produce the lower molecular weight components.

[0057] The present invention further relates to a catalyzed organicreaction process, the improvement which comprises:

[0058] conducting the reaction with a catalyst which is selected fromthe group consisting of a porous structured aluminosilicate,gallosilicate, titanosilicate and mixtures thereof which catalystcomprises: a framework of linked tetrahedral SiO₄ and AlO₄, GaO₄ or TiO₄units, the framework defining pores and having an Si to combined Ga, Tiand Al molar ratio of between about 1000 to 1 and 1 to 1, and having atleast one X-ray diffraction peak corresponding to a basal spacingbetween about 2 and 100 nm, and wherein the composition retains at least50% of initial framework pore volume after exposure to 20 volume % steamat 600° C. for four hours.

[0059] The present invention further relates to a porous structuredsilicate composition which comprises:

[0060] a framework of linked tetrahedral SiO₄ and units selected fromthe group consisting of AlO₄ units, GaO₄ units, TiO₄ units and mixedunits, the framework defining pores and having an Si to combined Ga, Tiand Al molar ratio of between about 1000 to 1 and 1 to 1, and having atleast one X-ray diffraction peak corresponding to a basal spacingbetween about 1 and 100 nm, and wherein the composition retains at least50% of the initial framework pore volume after exposure to 20 volumepercent steam at 600° C. for four hours.

[0061] The present invention further relates to a process for forming aporous aluminosilicate composition which comprises:

[0062] (a) providing zeolite fragments prepared by disrupting thestructure of a crystalline aluminosilicate zeolite in a form selectedfrom the group consisting of an aqueous solution, gel, suspension,wetted powder, and mixtures thereof;

[0063] (b) mixing in a mixture the zeolite fragments in an aqueousmedium with an organic porogen;

[0064] (c) aging the mixture of step (b) at a temperature between 25°and 200° C. to obtain a precipitate of the composition; and

[0065] (d) separating the composition from the mixture of step (c).

[0066] The compositions of the present invention can be used forhydroprocessing of petroleum, especially hydrocracking processes whereinpetroleum fractions, for example, distillates or resid fractions, arecracked to lower molecular weight fractions of useful hydrocarbons inthe presence of hydrogen gas. The beds for the catalytic cracking can befluidized. Usually the beds for hydrocracking are fixed.

[0067] Zeolites: are open framework aluminosilicate structures with longrange atomic order. They exhibit x-ray diffraction patternscharacteristic of the atomic order.

[0068] Protozeolitic Seeds are nanoclustered ions or molecules thatnucleate the crystallization of zeolites. They do not exhibit x-raydiffraction patterns indicative of long range atomic order. However,they contain zeolitic subunits that constitute the building blocks ofthe zeolite that they nucleate. The nanoclusters are formed fromsilicate and aluminate anions in the presence of inorganic ions (e.g.,sodium ions) or organic ions (e.g., onium ions) as structure directingagents.

[0069] Zeolite Fragments, as defined in the present art, are formedthrough the degradation of a crystalline zeolite, either by chemicalmeans (e.g., by treatment of the zeolite with a basic reactant) or byphysical means (e.g., through the input of energy such as ultra sound ormechanical energy in the form of grinding and milling). The long rangeatomic order of the initial zeolite is disrupted, as evidenced throughthe disappearance of some or all of the x-ray diffraction lines of thestarting zeolite. However, the zeolitic subunits that formed thebuilding blocks of the initial zeolite are still present in the zeolitefragments and these building blocks impart the desired steam stabilityto the aluminosilicate mesostructure that is formed when the fragmentsare assembled into the said open framework aluminosilicate mesostructurein the presence of a surfactant or porogen.

[0070] An organic porogen is an organic molecule which acts to formmesopores in the aluminosilicate composition. The porogen is an organicmolecule which is typically an amphiphilic surfactant, but organicmolecules that lack surfactant properties may also function as aporogen. A co-surfactant can be used to augment the surfactant. Theremoval of the porogen from the as-made composition allows the mesoporesto be accessed by other guest molecules for adsorption and chemicalcatalysis.

BRIEF DESCRIPTION OF DRAWING

[0071]FIG. 1 provides the ²⁷Al MAS NMR spectra for the as-made andcalcined (540° C.) forms of a 2%Al-MCM-41 aluminosilicate mesostructureprepared from conventional aluminate and silicate precursors. The arrowpoints to the resonance near 0 ppm that is indicative of six-coordinatedAlO₆ centers in the calcined mesostructure.

[0072]FIG. 2 provides the ²⁷Al MAS NMR spectra for aluminosilicatenanoclusters that act as nucleation centers (seeds) for the nucleationof faujasitic zeolite Y (denoted 10%Al-Y) and the nucleation of MFIzeolite ZSM-5 (denoted 5%Al-ZSM-5).

[0073]FIG. 2A provides the X-ray powder diffraction patterns for thesolids formed by air drying the zeolite Y seeds (denoted 10%Al-Y-Seeds)and by precipitating the zeolite Y seeds through the addition of ethanol(denoted 10Al-Y-Seeds+EtOH).

[0074]FIG. 3 is the XRD pattern for a 20%Al-MSU-S hexagonalaluminosilicate mesostructure that has been calcined at 540° C.

[0075]FIG. 4 provides the ²⁷Al-MAS NMR spectra for calcined forms ofAl-MSU-S aluminosilicate mesostructures and for the proton form ofzeolite Y (denoted HY). The chemical shift value of 62 ppm is indicativeof tetrahedral AlO₄ centers with a zeolite-like connectivity to SiO₄centers. No octahedral AlO₆ centers with a chemical shift near 0 ppm areindicated.

[0076]FIG. 5 provides the XRD patterns of a calcined cubic 10%Al-MSU-Saluminosilicate mesostructure assembled from nanoclustered zeolite Yseeds and a calcined cubic 2%Al-MCM-48 prepared from conventionalaluminate and silicate precursors.

[0077]FIG. 6 provides the ²⁷Al MAS NMR spectra for 2%Al-MSU-S preparedfrom zeolite Y seeds and 2%Al-MCM-41 prepared from conventionalprecursors. The arrow points to the resonance line near 0 ppm indicativeof AlO₆ centers.

[0078]FIG. 7 provides a transmission electron micrograph for a10%Al-MSU-S_(W) wormhole structure assembled from zeolite Y seeds.

[0079]FIG. 8 provides the nitrogen adsorption/desorption isotherms for2%Al-MSU-S and 10%Al-MSU-S_(W) wormhole structures assembled fromzeolite ZSM-5 and zeolite Y seeds, respectively. The insert provides theBET surface areas (S_(BET)) and pore volumes (P.V.) derived from theisotherms. Isotherms are offset by 200 cc/g for clarity.

[0080]FIG. 9 provides the XRD patterns for mesoporous aluminosilicates10% Al-MSU-S (assembled from zeolite Y seeds) and 2%Al-MSU-S (assembledfrom zeolite ZSM-5 seeds) with wormhole framework structures.

[0081]FIG. 10 provides the XRD patterns for 20%Al-MSU-S, 10%Al-MSU-S and2%Al-MCM-41 aluminosilicate mesostructures after having been exposed to20 vol % steam at 800° C. for 5 hours.

[0082]FIGS. 11A, 11B and 11C provide the XRD patterns (11A), andnitrogen adsorption/desorption isotherms (11B) for a freshly calcined“ultrastable” 14% Al-MCM-41 aluminosilicate prepared by graftingreaction of a secondary silica mesostructure with Al₁₃ oligocationsaccording to the method of Mokaya (Angew. Chem. Int. Ed. 38 No. 19, 2930(1999)) and for the same mesostructure after exposure to 20 vol % steamin nitrogen at 800° C. for 5 hours. Also, included in the figure is the²⁷Al AS NMR spectrum (11C) for the sample after exposure to steam.

[0083]FIGS. 12A and 12B provide XRD patterns of calcined (540° C., 7 h)mesoporous aluminosilicate molecular sieves before (12A) and after (12B)exposure to 20 vol % steam in nitrogen at 800° C. for 5 h): (A)hexagonal 10%Al-MSU-S prepared from zeolite Y seeds; (B) “ultrastable”hexagonal 14%Al-MCM-41 prepared by the grafting method of Mokaya (Angew.Chem. Int. Ed., 38 No. 19, 2930 (1999)); (C) disordered 10%Al-MCM-41prepared by direct synthesis from conventional silicate and aluminateprecursors. The intensity scale is the same for the samples before andafter steaming. The BET surface areas and pore volumes observed beforeand after exposure to steam at 800°, along with the hexagonal unit cellparameters are provided in Table 1.

[0084]FIGS. 13A and 13B provide the N₂ adsorption/desorption isothermsfor calcined (540° C., 7 h) mesoporous aluminosilicate molecular sievesbefore (13A) and after (13B) exposure to steam (20 vol % H₂O in N₂) at800° C. for 5 h: (A) hexagonal 10% Al-MSU-S; (B) “ultrastable”14%Al-MCM-41 prepared by the grafting method of Mokaya; (C) 10%Al-MCM-41prepared by direct synthesis from conventional precursors. Isotherms areoffset by 200 cc/g for clarity.

[0085]FIG. 14 is a graph showing cumene conversions over mesoporousaluminosilicates in the temperature range 300-450° C.: (A and C)conversions obtained for calcined and steamed samples of 10% Al-MSU-S,respectively; B and D) conversions for calcined and steamed samples,respectively, for 10% Al-MCM-41 prepared by direct synthesis. Reactionconditions: 6 mm i.d. fixed bed quartz reactor; 200 mg catalyst; cumeneflow rate, 4.1:mol/min; N₂ carrier gas, 20 cc/min; conversions reportedafter 30 min on steam.

[0086]FIG. 15 provides the infrared absorption spectra in the region 400to 800 cm⁻¹ for 5% Al-MCM-41 prepared from conventional precursors andfor 2%Al-MSU-S prepared from zeolite ZSM-5 seeds. Included forcomparison is the spectrum of an authentic sample of ZSM-5.

[0087]FIG. 16 is a graph showing IR spectra (KBr) of powdered forms of(A) zeolite ZSM-5 seeds prepared in the presence of TPA⁺ as template (B)zeolite Beta seeds prepared from TEA⁺ as template and (C) conventionalaluminosilicate anions prepared using TMA⁺ in place of TPA⁺ or TEA⁺.

[0088]FIGS. 17A, 17B and 17C are graphs showing XRD patterns of calcined(550° C., 4 h) mesoporous aluminosilicate molecular sieves before (A)and after (B) exposure to 20% steam at 600° C. and 800° C. for 5 h: (A)hexagonal 1.5% Al-MSU-S_((MFI)) prepared from zeolite ZSM-5 seeds; (B)hexagonal 1.5% Al-MSU-S, prepared from zeolite Beta seeds. The intensityscale is the same for the samples before and after steaming. Hexagonalunit cell parameters are provided in Table 2.

[0089]FIGS. 18A and 18B and 18C are graphs showing N₂adsorption/desorption isotherms for calcined (550° C., 5 h) hexagonalmesoporous aluminosilicate molecular sieves before and after steaming(20 vol % H₂O in N₂, 600° C., 5 h): (A): 1.5% Al-MSU-S from zeoliteZSM-5 seeds (B): 1.5%Al-MSU-S from zeolite beta seeds; (C): 1.5%Al-MCM-41 from conventional precursors. The isotherms are offset by 200cc/g for clarity.

[0090]FIG. 19 is a graph showing IR spectra of calcined hexagonalmesostructures: (A) 1.5%Al-MSU-S assembled from zeolite ZSM-5 seeds; (B)1.5%Al-MSU-S assembled from zeolite Beta seeds; and (C) 1.5%Al-MCM-41formed from conventional aluminosilicate precursors.

[0091]FIG. 20 is a graph showing XRD patterns of a hexagonal MSU-Saluminosilicate mesostructure (Si/Al=49) before (A) and after (B)steaming at 800° C. for 2 h. The composition was prepared from a mixtureof zeolite Y seeds (Si/Al=5.67) and sodium silicate in the presence ofPLURONIC P123™ surfactant.

[0092]FIG. 21 is a graph showing N₂ adsorption and desorption isothermsof a MSU-S aluminosilicate mesostructure (A) before and (B) aftersteaming at 800° C. for 2 h. The composition was assembled from amixture of zeolite Y seeds and sodium silicate in presence of PLURONICP123™ surfactant.

[0093]FIG. 21A shows the pore size.

[0094]FIG. 22 is a graph showing XRD patterns of the calcined product ofExample 23.

[0095]FIG. 23 is a graph showing N₂ adsorption and desorption isothermsof the calcined product of Example 23.

[0096]FIG. 23A shows the pore size.

[0097]FIG. 24 is a graph showing N₂ adsorption and desorption isothermsof the calcined product of Example 24.

[0098]FIG. 24A shows the pore size.

[0099]FIG. 25 is a graph showing N₂ adsorption and desorption isothermsof aluminosilicate compositions of the calcined aluminosilicatecompositions of Example 25 with cellular foam framework structurescontaining (A) 2 mole % Al and (B) 5 mole % Al.

[0100]FIG. 25A shows the pore size.

[0101]FIG. 26 is a graph showing N₂ adsorption and desorption isothermsof calcined aluminosilicate cellular foam composition of Example 26(Si/Al=67) (A) after calcination in air at 600° C. and (B) afterexposure to 20% steam at 600° C. for 4 h and (C)) after exposure to 20%steam at 800° C. for 2 h.

[0102]FIG. 26A shows the pore size.

[0103]FIGS. 27A and 27B are graphs showing N₂ adsorption and desorptionisotherms of calcined mesoporous aluminosilicate cellular foams(Si/Al=50) (FIG. 27A) before and after (FIG. 27B) exposure to 20% steamat 650° C. for 4 h: (A) prepared from ZSM-5 seeds, (B) zeolite Betaseeds and (C) conventional precursors.

[0104]FIG. 28 is a graph showing N₂ adsorption and desorption isothermsof the calcined product of Example 29.

[0105]FIG. 28A shows the pore size distribution.

[0106]FIG. 29 is a graph showing XRD patterns of the supermicroporousaluminosilicate composition of Example 30 (A) before and (B) aftersteaming at 650° C. for 4 h.

[0107]FIG. 30 is a graph showing N₂ adsorption and desorption isothermsfor the calcined supermicroporous compositions of Example 30 (A) beforeand (B) after exposure to 20% steam 650° C. for 4 h.

[0108]FIG. 30A shows the pore size.

[0109]FIG. 31 provides a sketch of the apparatus used for exposing thealuminosilicate structures to 20% steam.

[0110]FIG. 31A is a partial enlarged view of the sample chamber.

[0111]FIG. 32 is a graph showing x-ray powder diffraction patterns forExample 31.

[0112]FIG. 33 is a graph showing the nitrogen adsorption/desorptionpattern for the composition of Example 31.

[0113]FIG. 33A is a graph showing the pore size distribution.

[0114]FIG. 34 is a graph showing the chemical shift characteristic of Yzeolites in Example 31.

[0115]FIG. 35 is a graph showing the x-ray powder diffraction patternsfor the composition for Example 32.

[0116]FIG. 36 is a graph showing the nitrogen adsorption/desorptionpattern for the composition of Example 32.

[0117]FIG. 37 is a graph showing x-ray powder diffraction patterns forExample 33.

[0118]FIG. 38 is a graph showing the nitrogen adsorption/desorptionpattern for Example 33.

[0119]FIG. 40 is a graph showing the x-ray powder diffraction patternsfor the composition of Example 34.

[0120]FIG. 41 is a graph showing the nitrogen adsorption/desorptionpattern for the composition of Example 34. FIG. 34A shows the pore sizedistribution of the composition.

[0121]FIG. 42 is a graph showing the adsorption/desorption pattern forthe composition of Example 35. FIG. 35A shows the pore size distributionof the composition.

[0122]FIG. 43 is a graph showing the x-ray powder diffraction patternsof the composition of Example 36.

[0123]FIG. 44 is a graph showing the adsorption/desorption pattern forthe composition of Example 36.

[0124]FIG. 45 is a graph showing the pore size distribution of thecomposition of Example 37.

[0125]FIG. 46 is a graph showing nitrogen adsorption/desorptionisotherms for the composition of Example 37.

[0126]FIG. 47 is a graph showing XRD patterns of MSU-S/ITQ (Example 38)before and after steaming at 800° C. for 2 hours.

[0127]FIG. 48 is a graph showing N₂ sorption isotherms of MSU-S/ITQ(Example 38) before and after steaming at 800° C. for 2 hours.

[0128]FIG. 49 is a TEM image of MSU-S/ITQ (Example 38).

[0129]FIG. 50 is a graph showing N₂ sorption isotherms of MSU-S/TEA(Example 39) before and after steaming for 2 hours.

[0130]FIG. 51 is a TEM image of MSU-S/TEA (Example 39) at 200 nm and at25 nm measuring scale.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0131] This invention provides structurally distinct families of largepore (supermicroporous), to very large pore (mesoporous), to exceedinglylarge pore (macroporous) aluminosilicates that are stable solid acidcatalysts under the harsh steaming conditions encountered in theregeneration of the catalyst in processes such as the refining ofpetroleum. This result has been achieved without added reagent orprocessing costs in comparison to the costs for producing conventionalaluminosilicate structures with framework pores in the same size range.The large framework pore sizes, which have average diameters in therange 1-100 nm for the purposes of this invention, make these newmaterials especially desirable as solid acid catalysts, especiallycracking catalysts or hydrocracking catalysts for the refining of “heavycrudes” containing very high molecular weight fractions.

[0132] One approach for making ultrastable aluminosilicatemesostructures is to prepare first a reaction mixture ofnanometer-sized, protozeolitic anionic aluminosilicate clusters thatcontain primarily four-coordinated aluminum and silicon as linkedtetrahedral AlO₄ and SiO₄ units in the presence of a structure-directingagent which is an organic porogen that generates the desirednanoclusters. These protozeolitic nanoclustered aluminosilicate anionsare then further linked into a porous framework structure throughsupramolecular assembly reaction in the presence of astructure-directing surfactant, most preferably a onium ion surfactantor a non-ionic surfactant. The onium ion surfactant can containammonium, phosphonium or arsonium ions in an organic molecule. Thenon-ionic surfactant can be a di-, tri-, or tetrablock co-polymer inwhich the hydrophilic segments are one or more polyethylene oxide chain(PEO)_(x) and the hydrophobic segments are polypropylene oxide chains(PPO)_(y) alkyl chains, polybutylene oxide chains, substituted arylgroups or mixtures thereof. Non-ion PEO surfactants marketed under thetrade names PLURONIC (BASF), TETRONIC (BASF), TRITON, TERGITOL (UnionCarbide), BRIJ, SORBATAN, etc. are useful non-ionic surfactants. Neutralamines also are useful structure-directing surfactants, particularly forthe assembly of wormhole and lamellar framework structures (Kim et al.,Science, 282 1302 (1998)). Co-surfactants are useful in expanding thesize of the structure-directing surfactant micelles and, hence, the poresize of the framework. Bolaform surfactants, such as HO(CH₂)₁₆N(CH₃)₃ ⁺are effective in the assembly of supermicroporous frameworks (Bagshaw etal., Chem. Commun. 533-534 (2000)). The choice of surfactant andoptional co-surfactant plays an important role in determining the openframework structure type of the steam-stable compositions of thisinvention. In general hexagonal, cubic, lamellar and disordered wormholeframework structures can be assembled from zeolite seed precursors. Inaddition, cellular foam structures are obtained from surfactant andco-surfactant emulsions in the presence of zeolite seeds. Still furthernon-surfactant organic molecules, such as triethanolamine, are capableof functioning as porogens for the formation of wormhole frameworkstructures with mesopores (see Chem. Comm 8, 713 (2001)).

[0133] The appended examples illustrate the assembly of several openframework structure types. Each structure type exhibits a characteristicx-ray diffraction pattern. In all cases, except for the wormholestructures formed from triethanolamine, each structure type exhibits atleast one reflection corresponding to a spacing of at least 2.0 nm. Thestructure type also is verified through high resolution transmissionelectron micrographs that image the framework walls and pores. Thewormhole mesostructures formed from triethanolamine lack awell-expressed low angle XRD peak, but the wormhole framework is clearlyevident from TEM micrographs.

[0134] The displacement of alkali metal ions, organic ions andsurfactant from the as-made structures provide a porous framework withunique thermal and hydrothermal stability in comparison to previouslydisclosed aluminosilicate structures. Most preferred are the porousstructures obtained by displacing the sodium ions, organic ions and someof the surfactant by treatment with a solution of ammonium ions (NH₄ ⁺).The calcination of these NH₄ ⁺-exchanged forms of the compositions attemperatures above about 500° C. removes residual surfactant andconverts the ammonium ions to protons, thus affording a stable solidacid for catalyzing a variety of organic chemical conversions,especially alkylation reactions, isomerization reactions, crackingreactions, hydrocracking reactions, and hydrotreating reactions. Theresulting acidic compositions can be easily incorporated as an activecomponent of a conventional catalyst particle to improve catalyticconversions. If the concentration of alkali metal ions present in theassembly process is low, then few such ions are incorporated into theas-made products. In this case a steam-stable product can be obtainedthrough the removal of the surfactant and optional co-surfactant bycalcination. This avoids the need for an ion exchange reaction to removethe alkali metal ions prior to or following the removal of thesurfactant.

[0135] In particular, an enhancement in the catalytic performanceproperties of FCC (fluidized bed catalytic cracking) and hydrocrackingcatalyst particles can be expected by incorporating into the particlematrix the steam-stable porous compositions of the present invention asa component capable of cracking a high fraction of the petroleum thatcomprises the resid or heavy end fraction of the petroleum. Thesesteam-stable compositions can also be used as a component in aheterogeneous acid catalyst for various chemical syntheses, includingacetal formation, aromatic alkylations, olefin dimerizations andoligomerization, esterifications of olefins and alcohols, alcoholesterifications, etherification of alcohols, hydration of olefins,isomerizations, transalkylations, transesterifications, hydrolysisreactions, among others. The steam stability is very important for thesecatalytic applications because it allows the spent catalyst to becleansed of deactivating by-products through calcination in air, aprocess that generates substantial steam.

[0136] The protozeolitic nanoclustered aluminosilicate anions used toform the stable mesostructures of this invention are known in the art ofzeolite chemistry as nucleating agents or, more generally, as “zeoliteseeds”. They are given this term because they can be crystallized into aspecific atomically ordered zeolite upon aging them as a solution, gel,or wet solid at elevated temperatures. In addition, some zeolite seedscan promote the nucleation and crystallization of a specific zeolitewhen they are added in small amounts to reaction mixtures of silicateand aluminate ions that would not normally form the desired zeolite ofinterest under equivalent conditions in the absence of the added seeds.In general, zeolite seeds can have two physical forms, namely, they canbe in the form of sub-micrometer crystalline particles of the samezeolite that they nucleate, or they can be amorphous nanoclusters insolution, gel or solvent-suspended form. The sub-micrometer forms areoften referred to as “crystalline seeds”, whereas the amorphousnanoclustered forms are often called “nucleating centers, gels,solutions, agents, etc.” and sometimes “amorphous zeolites”. Forinstance, Lechert et al. Stud. Surf. Sci. Catal., 84,147(1994)distinguishes between “crystalline” and “amorphous gel” forms ofnucleating agents for type Y zeolites seeds. For the purpose ofpresenting the art of the present invention, however, we refer to bothforms of these zeolite nucleating reagents as “zeolite seeds” or simply“seeds” whether they are sub-micrometer crystals or amorphousnanoclusters.

[0137] In general, the preferred zeolite seed compositions used toassemble the steam-stable porous structures of this invention have lessthan about 5% of the linked SiO₄ and AlO₄ tetrahedra in atomicallycrystalline form, as judged from the integral intensities of the BraggX-ray reflections in comparison to a fully crystallized zeolite with thesame Bragg reflections. The most preferred zeolite seeds used to formthe steam-stable aluminosilicate compositions of this inventiontypically show no Bragg X-ray reflections either in aqueous suspensionor in powdered form.

[0138] Also, the preferred steam-stable supermicroporous (1.0-2.0 nm),mesoporous (2.0-50 nm) and macroporous (50-100 nm) aluminosilicateframework structures of this invention, do not exhibit Bragg X-rayreflections characteristic of an atomically ordered zeolite with longrange atomic order that persists over many crystallographic unit cells.However, the possibility that an atomically ordered zeolite phase can beadmixed with the steam-stable porous aluminosilicate compositions ofthis invention is not excluded. The presence of a mesoporousaluminosilicate phase is typically indicated by at least one X-raydiffraction peak corresponding to a basal spacing or pore to porecorrelation distance greater than about 2.0 nm, although the correlationlength is usually greater than 3.0 nm. The open framework structure isverified by transmission electron microscopy images that reveal a porenetwork and by nitrogen adsorption isotherms characteristic of pores inthe 1.0-100 nm range. The absence of long range atomic order in thewalls defining the framework pores is verified by the absence of narrowX-ray diffraction peaks corresponding to atomic order that repeats orpersists over many crystallographic unit cells. Short range atomic ordercorresponding to zeolitic subunits or building blocks is present in theframework walls and thus short range order can give rise to broadenedXRD diffraction peaks that reflect this short range atomic order.

[0139] All of the open framework aluminosilicate structures of thisinvention retain at least 50% of their initial framework surface areaand framework pore volume after exposure to 20 volume % steam at 800° C.for a period of 2 hr. No other previously disclosed open frameworkaluminosilicate compositions exhibit comparable hydrothermal stability.The main distinction between the art of this invention and allpreviously disclosed art for the assembly of open frameworkaluminosilicate compositions lies in the choice of silicate andaluminate precursors for the supramolecular assembly process. Whereas,the art of the present invention makes use of protozeoliticaluminosilicate nanoclusters or “zeolite seeds” and, as discussed below,“zeolite fragments”, for the assembly of the framework walls, allpreviously disclosed art utilized conventional silicate and aluminateprecursors.

[0140] Zeolite seeds are formed by aging mixtures of silicate anions andaluminate anions under conditions of basic pH and, normally, elevatedtemperatures in the presence of specific inorganic and organic cations.The cations are selected so that they act as “templates” or, moreprecisely, as structure directors in forming the seeds. For example, theuse of inorganic sodium cations to form seeds of zeolite Y, moreprecisely the seeds of faujasitic zeolites, has been disclosed by RobsonACS Sym. Ser.,398,436 (1989), by Vaughan et al, U.S. Pat. No. 4,178,352(1979), Lechert et al, Stud. Sur. Sci. Catal., 84, 147 (1994), and by USPatents 3,574,538 and 3,808,326 to McDaniel et al, U.S. Pat. No.3,671,191 to Maher et al. and U.S. Pat. No. 3,789,107 to Elliott. Theuse of organic cations to form seeds of many different families ofzeolites have been described by Lok et al. Zeolites, 3, 282 (1983); J.N. Watson et al. J. Chem. Soc., Faraday Trans. (94) 2181 (1998);P.P.E.A. de Moor, et al. Chem. Mater. (11) 36 (1999); P.P.E.A. de Moor,et al. J. Phys. Chem. B (103) 1639 (1999) and S. I. Zones et al.,Microporous Mesoporous. Mater. 21, 199(1998).

[0141] The structures of amorphous nanoclustered seeds is unknown, butit is presumed that the nanoclusters contain linkages of SiO₄ and AlO₄tetrahedra that resemble the secondary building blocks found incrystalline zeolites. These secondary building blocks may contain ringsof a specific number of space filling oxygen atoms that bridge thetetrahedrally coordinated silicon and aluminum centers, such as singleand double 4-rings, 5-rings, 6-rings, and the like, where the numbersrefer to the oxygenation in the ring. Whatever the connectivity of theSiO₄ and AlO₄ units in nanoclustered aluminosilicate seeds may be, theyare powerful structure-directing reagents in the nucleation of zeolitephases. The nanoclusters may be regarded as being “proto-zeolitic” bybearing a structure or tetrahedral building block connectivity thatreadily promotes zeolite crystallization. The art of the presentinvention discloses that these same protozeolitic seeds are preferredprecursors for the supramolecular assembly of highly stable structuredaluminosilicate molecular sieves, even though the framework walls remainlargely disordered in comparison to the atomically well-orderedframework walls of conventional zeolites. However, as noted above we donot exclude from the disclosed art the use of crystalline sub-micronzeolite seeds as precursors to the assembly of stable structuredaluminosilicate molecular sieves. Such small crystalline zeolite seedscan be transformed, at least in part, into stable framework wall-formingsubstructures under the conditions used to assemble an open frameworkstructure.

[0142] The structural order, acidity and steam stability ofaluminosilicate mesostructures all can be substantially improved throughthe assembly of nanoclustered precursors that normally nucleate thecrystallization of microporous zeolites, particularly zeolites type Yand ZSM-5. These zeolite seeds are presumed to promote zeolitenucleation by adopting AlO₄ and SiO₄ tetrahedra connectivities thatresemble the secondary structural elements in a crystalline zeolite.Assembling these same zeolite seeds into a mesostructure imparts acidityand hydrothermal stability that begin to approach zeolites, even thoughthe framework walls remain in large part atomically disordered.

[0143] The assembly of hydrothermally stable aluminosilicatemesostructures from zeolite seeds according to the teachings of thisinvention is not limited to zeolite Y formed from inorganic cations orto zeolite Beta or ZSM-5 zeolite seeds formed from organic cations. Anyzeolite seed composition can be used to form aluminosilicatemesostructures with a hydrothermal stability that is substantiallyimproved in comparison to the same mesostructures prepared fromconventional precursors. As we have noted above, the literaturediscloses numerous examples of organic molecules and ions that organize(or “template”) silicate and aluminate anions into nanoclustered unitsthat seed the nucleation of crystalline zeolites (see, for example, B.M. Lok, et al. Zeolites (3) 282 (1983); R. E. Boyett, et al., Zeolites(17) 508 (1996); S. I. Zones, et al. Microporous Mesoporous Mater. (21)199 (1998)). All of these protozeolitic seed compositions formed fromorganic templating agents are preferred precursors for thesurfactant-directed supramolecular assembly of aluminosilicatemesostructures with enhanced hydrothermal stabilities.

[0144] The assembly of zeolite seeds, particularly amorphousnanoclustered seeds, into a mesoporous framework causes the frameworkaluminum to remain in large part tetrahedral as AlO₄ units corner sharedwith silicate tetrahedra, even after calcination. Also, the siting ofthe aluminum is more like that found in a hydrothermally stable zeolite,as indicated in part by the aluminum nmr chemical shift or by certainabsorption bands in the infrared spectrum. Up to 35 mol % aluminum canbe easily incorporated into mesostructured aluminosilicate frameworks byutilizing zeolite Y seeds. Up to 13% Al was incorporated into aluminosilicate mesostructures formed from ZSM-5 zeolite seeds or zeolite Betaseeds. In principle it is possible to incorporate zeolite seedscontaining a 1:1 ratio of SiO₄ and AlO₄ tetrahedral units into amesostructure. For instance zeolite Type A (abbreviated LTA) can have upto 50% of the framework tetrahedral sites occupied by aluminum in placeof silicon. Importantly, for the porous aluminosilicate compositions ofthis invention typically more than 75% or even more than 90% of thealuminum sites remain tetrahedral after calcination at 540° C. ²⁷Al-NMRchemical shift of mesostructures formed from zeolite Y seeds, as well asthe shape and width of the resonance, was very similar to that ofmicroporous zeolite Y. This result indicates that the local environmentof the aluminum is analogous to that found in one of the most stable andmost widely used zeolites in the petrochemical industry. Thus, these newultrastable mesostructures are very useful for many applications wherezeolite Y and other zeolites cannot be used because of a limited poresize below 1.0 nm. In addition, the mesostructures remain porous evenafter treatment in 20% steam at 800° C. for up to 5 hours, making themsuitable for cracking or hydrocracking of high molecular weightpetroleum fractions that cannot be processed by zeolite Y.

[0145] Aluminosilicate mesostructures with Si/Al ratios greater thanabout 6.7 have been assembled from aluminosilicate nanoclusters thatnormally nucleate the crystallization of zeolites type Beta and ZSM-5.The aluminum content can be made very low by increasing the Si/Al ratioto 1000 and beyond. At Si/Al ratios beyond 1000 the mesostructures arefor all intents and purposes essentially silica rather thanaluminosilicate mesostructures. Most silicate precursors used for thepreparation of zeolite seeds contain aluminum as an impurity at the onepart per thousand to one part per ten thousand level. The calcinedmesostructures assembled from zeolite Beta and ZSM-5 seeds are stable to20% steam at 800° C. for 4 hours. The intrinsic acidity of thesemesostructures is sufficient to crack cumene over the temperature range300-450° C., suggesting that nanoclustered zeolite seeds are promisingprecursors for the design of hydrothermally stable mesostructures forthe acid-catalyzed processing of high molecular weight petroleumfractions that cannot be adequately refined over microporous zeolites.

[0146] Several structurally relevant properties embody the stablemesostructured aluminosilicate compositions of this invention anddistinguish them from previously disclosed mesostructures. In onegeneral structural embodiment of the invention, the preferredcompositions prepared from zeolite seeds templated by inorganic cations(e.g., sodium) have an experimentally observed ²⁷Al MAS NMR chemicalshift in the range 57-65 ppm relative to an aqueous 1.0 M aluminumnitrate as an external chemical shift reference. This is the chemicalshift range that is found for many crystalline zeolite, includingzeolite Y and other faujasitic zeolites. All previously reportedmesostructured aluminosilicates prepared from conventional silicate andaluminate precursors, including the original Al-MCM-41 compositions ofBeck et al., exhibit a chemical shift of 53-56 ppm. Chemical shiftvalues in the range of 57-65 ppm are indicative of a zeolite-likeconnectivity of the SiO₄ and the AlO₄ units that comprise the frameworkwalls of the mesostructures, even though the framework walls are largelydisordered. We postulate that the zeolitic connectivity of the saidtetrahedral units mimic the structural subunits of a zeolite and therebycontributes substantially to the improvement in the hydrothermalstability of these preferred mesostructured compositions.

[0147] As another structural distinction, the ²⁷Al MAS NMR chemicalshifts of several of the preferred compositions fall in the range ofpreviously disclosed mesostructured aluminosilicate compositions, forexample, 53-56 ppm, but are distinguished by the presence of an infraredadsorption band in the frequency range 500-600 cm⁻¹ in the case ofpentasil zeolite seeds wherein rings containing five oxygen atoms arepresent. The most universal structural distinction, however, is providedby the retention of at least 80% of the initial framework mesoporevolume is retained when the composition is exposed to boiling water for5 hours or to 20% steam at 600° C. for 5 hours. The infrared band at500-600 cm⁻¹ is indicative of the presence of pentasil zeolite in theamorphous framework walls. These compositions also are stable to 20%steam at 800° C. for 2 hr, retaining more than 50% of the frameworksurface area and pore volume observed prior to exposure to steam underthese conditions. Pentasil zeolite seeds, particularly those of zeolitesZSM-5, ZSM-11, and Beta are especially effective in providing thesteam-stable compositions characterized by the said second structuralembodiment.

[0148] Yet another structural distinction, the preferred aluminosilicatecompositions of this invention are free of sodium exchange cations,exhibit a zeolite-like ²⁷Al MAS NMR chemical shift in the range 57 to 65ppm, and contain between 0.01 and 10 wt % carbon embedded in theframework mesopores. The sodium ions in the as-made mesostructures aredisplaced by ion exchange reaction with an ammonium salt, mostpreferably ammonium nitrate, in aqueous solution in the presence of thestructure directing surfactant in the framework mesopores This exchangereaction also displaces a substantial amount of surfactant from themesopores. Subsequent to the ion exchange reaction with ammonium ions,the mesostructure is calcined in air at a temperature sufficient toremove the remaining surfactant and to convert the ammonium exchangeions to protons, most preferably at a temperature of 540° C. for aperiod of about 5 hours. This calcination procedure converts some of theremaining framework surfactant to carbon, presumably through crackingreactions of the surfactant in the acidic mesopores of the framework.The embedded carbon, which can amount to 0.01 to 10 wt % of the calcinedmesostructure depending on the calcination conditions used to degradethe intercalated porogen, can play an important role in the hydrothermalstability of the mesostructures, presumably by reinforcing the frameworkagainst collapse under hydrothermal conditions. Even more carbon (e.g.up to 50 wt % or more) can be loaded into the framework pores by firstintercalating a carbon precursor into the pores such as sucrose,furfuryl alcohol, a formaldehyde-phenolic resin or divinyl benzene, andthen pyrolyzing the precursor in the pores (see J. Am. Chem. Soc. 122,10712; J. Phys. Chem. B, 103, 7743 (1999); Chem. Comm. 559, (2001); J.Am. Chem. Soc., 123 5146 (2001)). In comparison to conventionalaluminosilicate mesostructures, the exceptional acidity of thealuminosilicate framework containing zeolitic nanoclusters promotesefficient carbon formation that more accurately replicates the structureof the aluminosilicate mold. Furthermore, the resulting carbon replicacan be recovered in pure form by dissolving away the aluminosilicatemold. The resulting carbon replicas are useful as adsorbents, doublelayer capacitors, and as supports for dispersed metal particles for usein chemical catalysis (see Chem. Comm. 2177 (1999); Nature 412, 169(2001)).

[0149] Yet another important feature of the art disclosed in thisinvention is the formation of steam-stable open framework structuresfrom mixtures of zeolite seeds and conventional silicate precursors. Astaught in appended Examples, zeolite seeds are effective in convertingconventional silicate precursors into protozeolitic nanoclusterssuitable for the supramolecular assembly of steam-stable open frameworkstructures. This feature of the art is very useful in forming especiallystable framework structures with high Si/Al ratios from zeolite seedsthat are best prepared at low Si/Al ratios. Zeolite type Y seeds, forexample, are best prepared at a Si/Al ratio below 10 in the presence ofNa⁺ ions as the template. By diluting the zeolite Y seeds withconventional sodium silicate precursors, one can assemble steam-stableopen framework structures with substantially higher Si/Al ratios (e.g.,Si/Al=50).

[0150] All of the structured aluminosilicate compositions of thisinvention share the common property of retaining at least 50% of theirinitial framework surface area and framework pore volume when exposed to20% steam at 800° C. for 2 hours. In general, however, the calcinedmesoporous aluminosilicate compositions of the present invention withhexagonal, cubic, lamellar and wormhole framework structure and poresizes in the range 2.0-500 nm are more stable to exposure to steam thanthe compositionally equivalent calcined compositions withsupermicroporous framework structures (1.0-2.0 nm) or with cellular foamstructures and framework pores of 10-100 nm. The said mesostructures arestable to 20% steam at 800° C. for 4 hr or even longer exposure times.Although the said supermicroporous and cellular foam aluminosilicatesretain at least 50% of their initial surface area and framework porevolume in 20% steam at 8000 after an exposure time of 2 h, they willrapidly degrade upon longer exposure times to steam under theseconditions. Nevertheless, the supermicroporous structures and cellularfoam structures of this invention have much longer useful lifetimes whenexposed to 20 volume % steam at 650° C. or, even better, when exposed to20% steam at 500° C. Under these latter steaming conditions they retainmore than 50% of their framework pore volume and framework surface areasafter exposure times longer than 4 hours. No other supermicroporous orcellular foam aluminosilicate composition formed through asupramolecular assembly pathway is known to survive exposure to 20%steam at 650° C. for equivalent periods of time.

[0151] Protozeolitic seeds of pentasil zeolites are especially valuablefor forming steam-stable aluminosilicate structures. At least threezeolite structure types, namely, ZSM-5, ZSM-11, and Beta and generallydescribed as MFI, MEL, and BEA structure types, respectively, aremembers of the pentasil family of zeolites. These structure types aretemplated by tetrapropyl, tetrabutyl, and tetraethyl ammonium ions,respectively. Moreover, the aluminum centers in these zeolites caneasily be substituted by gallium and titanium, producing analogous MFI,MEL and BEA gallosilicate and titanosilicates with Si/Ga and Si/Tiratios in the range 1000 to about 10 and, more preferably, about 100 toabout 20. Therefore, the art of the present invention may also be usedto assemble hydrothermally stable hexagonal, cubic, lamellar, wormholeand cellular foam framework structures of gallosilicates with Si/Ga andSi/Ti ratios in the range 1000 to about 10. For instance, thenanoclustered seeds of a MFI or BEA gallosilicate are readily preparedaccording to Examples 3, 20, and 21 simply by replacing sodium aluminatewith sodium gallate, gallium chloride or gallium nitrate. It is alsopossible to prepare MFI or BEA gallosilicate or titanosilicate seedssimply by replacing the aluminum alkoxide in Example 27 with a galliumalkoxide or a titanium alkoxide and adjusting the digestion time to 3-10hr. The resulting seeds can then be assembled into the desired steamstable wormhole, hexagonal, cubic, lamellar or cellular foam frameworkstructures according to Examples 12, 18, 20, 21, 27, among others, withpore sizes in the range 1-100 nm and Si/Ti and Si/Ga ratios in the range1000 to about 10.

[0152] In view of the importance of the ²⁷Al MAS NMR chemical shiftmeasurements in characterizing the preferred compositions embodied inthis invention, we briefly describe the measurement of this diagnosticparameter. In magic angle spinning (MAS) nuclear magnetic resonance(NMR) spectroscopy experiment, the energy levels of the magnetic nucleusare split by the imposed magnetic field. Transitions between theseenergy levels are made to occur through the absorption ofelectromagnetic radiation in the radio frequency range, typically themegahertz range. The absorption of the electromagnetic radiation givesrise to a “resonance” line at a frequency that is energeticallyequivalent to the energy separation between the magnetic energy levelsfor the nucleus under investigation. The sample is spun at an angle tothe imposed magnetic field (the so-called magnetic angle) to average-outdipolar interactions that can broaden the resonance lines and complicatethe spectrum. Because the electrons surrounding the nucleus contributeto the magnetic field experienced by the nucleus, the resonancefrequency is dependent on the chemical environment. Thus, the resonancefrequency “shifts”, depending on the chemical environment. These“chemical shifts” in the resonance frequency are recorded in “parts permillion” (ppm) frequency units relative to the frequency of a referencecompound with a known chemical environment and an arbitrarily assignedchemical shift of 0 ppm. The magnitude of the chemical shift is oftenused to deduce information on the chemical environment of the nucleus inthe chemical compound being studied by MAS NMR.

[0153] In the case of quadrupolar ²⁷Al nuclei, the splitting of thenuclear energy levels is determined by the nuclear magnetic spin quantumnumber I=5/2. The observed MAS NMR spectrum is typically dominated bythe (+½, −½) central transition. The experimentally observed chemicalshift for the resonance line corresponding to this transition can beinfluenced by quadrupolar interactions of the nucleus with the electricfield gradient at the nucleus. Generally speaking, the observed ²⁷Al MASNMR chemical shifts should be corrected for quadrupolar interactions toobtain the true values of the chemical shifts. However, if the electricfield gradient at the nucleus is small, then the error in the observedresonance position for the (+½, −½) transition also is small (about 1ppm or so in error) and no correction in the observed chemical shift isneeded, especially if the differences in the chemical shifts beingcompared are much larger than the error caused by quadrupolar effects.This is typically the case for the AlO₄ tetrahedra in most zeolites andrelated aluminosilicates (see Lippmaa et al., J. Amer. Chem. Soc. 1081730 (1986)), as well as for the Al(H₂O)₆ ³⁺ cations that are used asthe chemical shift reference in ²⁷Al NMR spectroscopy. For this reason,the chemical shifts reported here and in the literature foraluminosilicate mesostructures are not corrected for quadrupolareffects.

[0154] In the present invention steam stable aluminosilicatemesostructures are produced using inorganic or organic zeolite seeds andprecursors along with a quaternary ammonium compound. The zeolite seedsare allowed to digest (age), typically at a temperature between about25° and 100° C. For the formation inorganic zeolite seeds (i.e., seedsformed from inorganic structure directors) the mole ratio of Si to Al isless than or equal to 10 (but greater than 1.0) in order to form themesostructures. For the organic zeolite seeds (i.e. seeds formed fromorganic templates) the ratio of Si to Al is greater than or equal to 10,more preferably greater or equal to 20. The result is that using theinorganic zeolite seeds formed from inorganic structure directors (i.e.,alkali metal ions) is a structure with a chemical shift of between about57 to 65 ppm. For the pentasil zeolite seeds made from organic templates(i.e., organic onium ions) the chemical shift is between about 53 and 56ppm, but unlike the seed made from inorganic templates, they alsoexhibit a distinct infrared absorption band in the region 500-600 cm⁻¹.

[0155] It is very important that the digestion occurs for a sufficientperiod of time (1 to 48 hours). A Bragg XRD is not obtained as with thefully formed zeolite so that the zeolite seeds are well formed at basicpH (pH 10 to 14).

[0156] If the pore forming surfactant and optional co-surfactant isadded too soon to the seeds solution, the result is an ordinaryaluminosilicate structure with limited or no steam stability. If thezeolite seeds are allowed to form (nucleate) completely then an ordinaryzeolite is formed which is microporous. The porous structures of thepresent invention are between about 1 and 100 nm in pore diameter andcan either have a hexagonal, cubic, lamellar, wormhole, or cellular foamframework structure. In any event the structures are steam stable.

[0157] The steam stabilities of our aluminosilicate structures have beencompared by virtually all of the general synthetic methods reported inthe literature. None is as stable to steam as those in the presentapplication. Although the steam stability of crystalline zeolitesgenerally decreases with increasing aluminum content, this may not betrue for amorphous aluminosilicate mesostructures that contain terminalSiOH groups. Aluminum may actually improve the framework crosslinking insuch mesostructures. For instance, a pure silica MCM-41 prepared in theabsence of sodium is not as hydrothermally stable as its Al-graftedanalog, and the hydrothermal stability increases with increasing Alcontent. The hydrothermal stability of this sodium-free, Al-graftedMCM-41 was checked and found it to be greatly inferior to MSU-Scompositions in hydrothermal stability. The Al content of the MFI andBEA seeds can be doubled to 3.0% without a discernable change in steamstability of the final mesostructures.

[0158] Thus the preceding description particularly describessteam-stable aluminosilicate mesostructures that were assembled fromzeolite seeds. Zeolite seeds are nanoclusters of aluminosilicate anionsthat nucleate the crystallization of specific zeolite phases. It wasdemonstrated that by capturing the protozeolitic nanoclusters prior totheir formation of a zeolite phase, one could use the nanoclusters toform mesoporous aluminosilicate mesostructures with exceptionalhydrothermal stabilities (denoted MSU-S) in comparison tocompositionally equivalent mesostructures assembled from conventionalsilicate and aluminate precursors. The improved hydrothermal stabilityof MSU-S aluminosilicates was attributable to the presence of zeoliticsub-units in the walls of mesostructures. Although the walls of thesteam-stable mesostructures remained atomically disordered (amorphous),the NMR and IR spectroscopic studies show that a substantial fraction ofthe SiO₄ and AlO₄ tetrahedra comprising the walls of the steam-stablemesostructures are linked together (i.e., co-polymerized) in a way thatincluded the subunits of a zeolite structure.

[0159] Further the aluminosilicate compositions can comprise a compositeof a steam-stable, mesoporous MSU-S mesostructure phase (pore size2.0-100 nm) and an atomically ordered (crystalline) and microporous0.4-2.0 nm zeolite phase. Zeolite phases may be described as being“microstructured” or “microporous” phases, because they are atomicallyordered open framework structures that provide pore sizes in the rangefrom about 0.4 to 2.0 nm. These composite materials were formed in atleast two different ways. One approach was to utilize the sameprotozeolitic seeds solutions and gels that are useful for the formationof MSU-S mesostructures, except that the seeds were allowed to mature tothe point where a zeolite phase is formed in part and then the remainingseeds are transformed into a MSU-S mesostructure to form the saidcomposite. Another approach was to transform a zeolite seeds solution orgel directly into a composite mixture of a mesostructure MSU-S phase anda crystalline zeolite phase. This later approach was achieved byarresting the crystallization of the zeolite seeds solution or gelthrough the addition of a mesostructuring surfactant and the carefulcontrol of the pH of the seeds solution or gel.

[0160] The ratio of mesostructured MSU-S to zeolite phases in thecomposite compositions can range from about 99:1 to 1:99. The compositephases are preferably those in which the fraction of the zeolite phasetypically represent less than 50% of the total composite by weight.Zeolite crystals tend to be small, often nanosized, at the beginning ofthe zeolite crystallization process. The dispersion of nanosized zeolitecrystals in a matrix of MSU-S mesostructure is highly desirable for theuse of the composites as heterogeneous catalysts and catalyst supports.By minimizing the size of the zeolite phase in the composite, thezeolite becomes highly dispersed in the MSU-S mesostructure matrix and,therefore, more accessible for catalytic reaction.

[0161] Especially preferred zeolite phases are those that are used asheterogeneous catalytic and adsorptive commercial processes. Zeolitephases that are used for the processing of petroleum and petrochemicals,particularly the faujasitic zeolitic type X and type Y as well as thepentasil zeolite phases (i.e., those containing rings made of five Si—Olinkages). Zeolites ZSM-5, Beta, and ZSM-11, are especially preferredpentasil zeolites. Also, the faujasitic phases, as represented byzeolites X and Y, are useful for petroleum refining, the trapping ofcontaminates from waste streams, and as agents for the separation ofmolecules, such as the separation of oxygen and nitrogen molecules ofair when the faujasite zeolite is in Li⁺ exchange from. The mesophorousMSU-S aluminosilicate mesophase may have hexagonal, cubic, lamellar, orwormhole framework structures. The cation exchange sites of both phasesmay be occupied by any desired organic, inorganic or complex cation toachieve a particular catalytic or adsorption result. Also, otherelements may be substituted for either silicon (e.g., titanium orgermanium) or for aluminum (e.g., gallium) in either the mesostructuredMSU-S or microstructured zeolite phase of the composite composition tofavorably alter the catalytic activity or adsorption selectivity of thecomposite. Still further, the said composite compositions can be blendedwith other matrix materials such as kaolin clay, metakaolin clay,alumina and numerous other matrix phases to form complex,multi-component mixtures for multi-functional catalysis and selectiveadsorption processes.

[0162] Naturally occurring clay kaolin is another highly preferredcrystalline aluminosilicate precursor that can be reconstituted into azeolite seeds solution or gel and used to prepare a mesostructuredMSU-S/microstructured zeolite composite or a pure MSU-S mesostructure.In this aspect of the present invention, the kaolin is calcined at atemperature above about 650° C. to form metakaolin and the metakaolincan be transformed into a zeolite seeds solution or gel for thepreparation of the desired MSU-S mesostructure or a mesostructuredMSU-S/microstructured zeolite composite composition.

[0163] A further aspect of the present invention is steam stable MSU-Smesostructures, whether formed as part of a mesostructuredMSU-S/microstructured zeolite composite or as a pure MSU-Smesostructure, which can be formed from crystalline zeolites or zeoliteprecursors. Thus, in this embodiment a crystalline zeoliticaluminosilicate, is transformed into a solution or gel of zeolitefragments. The zeolitic aggregates were then transformed into a steamstable MSU-S mesostructure or a composite MSU-S/zeolite composition.Especially preferred crystalline aluminosilicates for the preparation ofa zeolite seeds solution or gel are the synthetic and naturallyoccurring zeolites themselves. Many naturally occurring zeolites or lowcost synthetic zeolites can be transformed into a zeolite fragmentsolution or gel through digestion in a basic aqueous solution (pH >10)or through a combination of thermal treatment and hydrolysis in basicaqueous solution. For instance, the faujasitic zeolites type X and typeY were transformed into a zeolite fragment solution by digestion insodium hydroxide solution. The said fragment solution then wassubsequently converted into an MSU-S mesostructure or a mesostructuredMSU-S/microstructured zeolite composite by adjusting the pH and adding astructure directing surfactant.

[0164] A “zeolitic fragment” differs from a “zeolite seed”. The formerreagent is generated through the breakdown of the long-range atomicorder of a crystalline zeolite, whereas the latter is an aluminosilicatenanocluster formed from silicate and aluminate ions in the presence of anucleating agent. A zeolite fragment, like a protozeolitic zeolite seed,contains zeolitic subunits or nanoclusters. Therefore, another approachto obtaining zeolitic subunits from zeolite precursors, other than thechemical approach described above, is to break down the zeolitestructure through the input of physical energy. The physical energyneeds to be sufficient in magnitude and duration to disrupt the longrange atomic order of the crystallized zeolite, but not so severe as todestroy all the subunit building blocks of the initial zeolite crystal.At the same time, the zeolite fragments cannot be so large as to preventtheir assembly into a mesostructure. The mechanical energy needed tobreak down the initial crystalline zeolite can be conveniently deliveredin the form of ultrasound or through milling and grinding. In addition,one can combine both physical energy and chemical transformationsimultaneously or in sequence to break down the long range atomicstructure of a zeolite to achieve zeolitic fragments suitable forassembly into a steam stable aluminosilicate mesostructure. There-assembly of the zeolitic fragments into a mesostructure is achievedthrough reaction with a structure-directing agent, typically asurfactant in micellar or liquid crystal form. The surfactant not onlyplays the role of a mesostructure director, but also a pore-former orporogen. Removal of the surfactant or porogen by solvent extraction orby mechanical means affords the desired open framework aluminosilicatemesostructure that is stable to steam.

[0165] The following Example 38 illustrates the use of mechanicalenergy, more precisely ultrasound energy, to break down the long rangeatomic energy of a zeolite precursor into zeolitic fragments suitablefor the assembly into a steam stable aluminosilicate mesostructure. Forinstance, the zeolite MCM-22 contains crosslinked lamellar units as partof its crystal structure. This zeolite is formed from a lamellaraluminosilicate precursor, denoted MCM-22(P) When the layers arecondensed in the direction orthogonal to the layers, the MCM-22 zeoliteis formed. The lamellae can have a lateral dimension as large as thecrystal itself (i.e., submicrons to microns in lateral width. Thelamellae of MCM-22(P) can be segregated by intercalation of a surfactantto give a pillared form, as demonstrated by the art of Mobilresearchers. (S. L. Lawton, A. S. Fung, G. J. Kennedy, L. B. Alemany, C.D. Chang, G. H. Hatzikos, D. N. Lissy, M. K. Rubin, H. J. C. Timken, S.Stenernagel, D. E. Woessner, J. Phys. Chem. 100 3788 (1996)). In thiscase the surfactant acts as a swelling or pillaring agent for thelamellar structure. The pillared derivatives of MCM-22(P) exhibit noveladsorption and catalytic properties in its own right. But the propertiesderived from a pillared MCM-22 (P) can be enhanced further by separatingthe layers of the pillared structure into unstacked or exfoliated forms,known as ITQ-2, as demonstrated by Corma and his co-workers (Nature 396353 (1998)). The delamination process results in the de-stacking orexfoliation of the pillared MCM-22(P) layers and this provides morefacile access to the layers for improved catalysis and adsorption. Inthe delaminated state of MCM-22(P), denoted ITQ-2 by Corma, the layeredunits retain their in-plane atomic structure. Consequently, thedelaminated layers still show XRD peaks indicative of the in-planeportion of the MCM-22 zeolite structure, but the XRD reflectionscharacteristic of layer-stacking are absent in the ITQ-2 derivative.

[0166] As shown by the art of the present invention, the delaminatedlayers of ITQ-2 can be broken down further into zeolitic fragments bythe application of sufficient ultrasound energy that goes beyond simplelayer delamination. The energy provided by ultrasound, if sufficientlyintense and long in duration, will actually cause fracture of the layersinto atomically disordered nanoparticles. The art of the presentinvention shows that the disordered nanoparticles or zeolite fragmentsobtained through mechanical degradation are suitable for assembly into asteam-stable mesostructure. The resulting fragments contain zeoliticsubunits, but the long-range in-plane atomic structure of the layers islargely lost, as evidenced by a loss of characteristic in-plane XRDpeaks. The resulting fragments can then be assembled by reaction with astructure-directing surfactant into a steam-stable mesostructure. Thedelaminated ITQ-2 layers produced in Corma's art, however, cannot bere-assembled into a mesostructure that exhibits a small anglediffraction peak.

[0167] The concept of using physical energy, as opposed to chemicalmeans, to break down the structure of a zeolite can be applied to anycrystalline zeolite or zeolite precursor structure to form analuminosilicate mesostructure with improved acidity and hydrothermalstability.

[0168] Yet another objective of this invention, as shown in Example 39,is to demonstrate that steam-stable mesostructures with wormhole-likealuminosilicate frameworks can be formed from zeolitic subunits usingsmall molecules as the pore-forming porogen in place of a surfactant.The group of Mashmeyer (J. C. Jansen, Z. Shan, L. Marchese, W. Zhou, vonder Puil, N. T. Mashmeyer, Chem. Comm. 8 713 (2001)) first disclosed theconcept of using small molecules, as such as triethanol amine, as apore-forming porogen for the formation of silicate mesostructures knownas TUD-1. The resulting mesostructured wormhole frameworks typically arenot sufficiently ordered to exhibit a small angle x-ray diffraction peakcharacteristic of most wormhole mesostructures, but the presence of awormhole framework structure nevertheless can be imagined by TEM. Thepore sizes, surface areas and pore volumes are comparable to those ofwormhole mesostructures that do exhibit a small angle diffraction peak.

[0169] In the present invention it is demonstrated that steam-stableanalogs of TUD-1 wormhole mesostructures can be prepared through theassembly of protozeolitic seeds in the presence of triethanol amine as aporogen. These assembled mesostructures are as stable to steam as theanalogous wormhole mesostructures assembled in the presence of asurfactant. A major difference between the wormhole framework structuresformed through surfactant templating and triethanol amine templating isthat the former structure exhibit a well expressed low angle X-rayreflection indicative of a well ordered mesostructure, whereas thewormhole framework formed in the presence of triethanol amine is lesswell ordered and exhibits little or no X-ray diffraction at low angles.The wormhole framework structures, however, are clearly revealed throughTEM imaging.

[0170] It is worth emphasizing the formal definition of the prefix“meso” relates to a length scale between 2.0 and 50 nm. Thus, a“mesostructure” is formally a structure that repeats on a length scalebetween 2.0 and 50 nm. Also, a “mesoporous” material has an average poresize between 2.0 and 50 nm. For the purpose of the present invention,however, we expand the meaning of “meso” to include a length scalebetween about 1.0 nm and 100 nm. Thus, a composition with an averagepore size of 1.5 nm is included in the description of a mesoporouscomposition, even though the composition would be regarded as a“supermicroporous” or simply a microporous material by IUPACdefinitions. Similarly, a composition with an average pore size of 80 nmcould be considered to fall within the INPAC definition of“macroporous”. The material is regarded as being “mesoporous” for thepurpose of defining the porous composition of the present invention.

[0171] With regard to the distinction between “zeolite seeds” and“zeolite fragments”, it is commented further as follows. As notedearlier, zeolite seeds are anionic aluminosilicate nanoclustersconstructed from simple silicate and aluminate ions in the presence ofan organic or inorganic structure directing cation. The distinguishingfeature of the aluminosilicate nanoclusters is their ability to nucleatethe crystallization of a zeolite with long range atomic order. The“zeolite seeds” are thus “protozeolitic nanoclusters” containingsubunits that resemble the structural building blocks of the crystallinezeolites that they nucleate. However, zeolite seeds lack the long rangeatomic order that is characteristic of a crystalline zeolite. That is,the atoms comprising a zeolite seeds are not constrained to occupyingspecific lattice points in three-dimensional space over manycrystallographic unit cells. Nevertheless, the relationship between thestructural subunits in a zeolite seed and in a crystalline zeolite canoften be verified by spectroscopic techniques such as infraredspectroscopy and NMR spectroscopy.

[0172] In contrast to zeolite seeds, “zeolite fragment” are formedthrough the breakdown of the long-range atomic order of a crystallinezeolite or zeolite precursor, such as zeolite Y or the precursor ofzeolite MCM-22, respectively. The breakdown in long-range atomic order,which can be accomplished by chemical or physical means, does not haveto be complete. That is, the x-ray or electron diffraction pattern mayexhibit some of the same reflections that are found in the startingzeolite or zeolite precursor, but several other reflectionscharacteristic of the starting zeolite or zeolite precursor will bemissing from the x-ray or electron diffraction pattern of the zeolitefragment. Thus, a zeolite fragment, like a zeolite seed, lacks longrange atomic order and contains subunits characteristic of the buildingblocks of a crystalline zeolite. However, a zeolite fragment is lessdisordered than a zeolite seed and is capable of exhibiting some, butnot all, of the x-ray or electron diffraction lines characteristic ofthe starting zeolite or zeolite precursor. The lack of long range atomicorder in zeolite seeds and zeolite fragments makes it possible toassemble these atomically disordered aggregates into mesostructuredaluminosilicates with framework pore sizes in the range 1.0-100 nm. Thepresence of zeolitic subunits in the mesostructures imparts valuablehydrothermal and steam stability.

[0173] Regarding the assembly of zeolite seeds into a steam-stablealuminosilicate mesostructure, it is pointed out that the pH value usedto form the zeolite seeds is especially important. Normally, zeoliteseeds are formed at pH values that are higher than the pH values neededto form an aluminosilicate mesostructure through supramolecular assemblyprocesses. Therefore, it is generally necessary to first form thezeolite seeds in the presence of the zeolite structure director at ahigh pH value (typically, above pH 11-12) and then lower the pH throughthe addition of acid to a value suitable for mesostructure formation(typically below pH about 11-12). This is why all previously reportedpreparations of aluminosilicate mesostructures have afforded materialswith comparatively poor steam stability even though a zeolite structuredirecting agent (e.g., sodium ion or an alkyl ammonium) ion may havebeen present in the reaction used to form the mesostructure. Mixing azeolite structure forming agent with a mesostructure forming agent underthe pH conditions needed to form the mesostructure will not impart thedesired steam stability to the mesostructure because the pH is too lowto form zeolite seeds.

COMPARATIVE EXAMPLE 1

[0174] In order to have a contrast example for our newly inventedaluminosilicate mesoporous molecular sieves, we prepared a conventional(well-ordered) hexagonal MCM-41 aluminosilicate molecular sieve in whichthe overall Si/Al molar ratio was 49/1. This Example 1 sample is denoted2% Al-MCM-41. The synthesis recipe was as follows: a solution containingthe appropriate amounts of sodium aluminate (NaAlO₂) and sodium silicatesolution was mixed, and then the required amount of H₂SO₄ acid was addedunder stirring to obtain a clear solution. Next, the required amount ofcetyltrimethyl ammonium bromide (CTAB) in water was added and themixture was stirred vigorous at ambient temperature for 30 minutes. Theresultant mixture was aged without stirring in a Teflon lined autoclaveat 100° C. for 2 days. The product was recovered by filtration andthoroughly washing with deionized water. The molar composition for thisparticular synthesis was:

[0175] 0.02 mole NaAlO₂

[0176] 1.0 mole sodium silicate solution (27 wt %)

[0177] 0.25 mole CTAB

[0178] 0.28 mole H₂SO₄

[0179] 130 mole H₂O

[0180] The initial solution compositions were as follows:

[0181] 6.56×10⁻⁴ mole sodium aluminate in 0.28 mole water

[0182] 3.28×10⁻² mole sodium silicate (27 wt % silica)

[0183] 8.20×10⁻³ mole surfactant in 3.9 mole water

[0184] 9.18×10⁻³ mole sulfuric acid in 0.08 mole water

[0185] The sample after calcination at 650° C. exhibited a BET surfacearea of 1037 m²/g, a total pore volume of 0.77 cc/g and an effectivepore size of 33 A as determined from the Horvath-Kawazoe model. TheX-ray diffraction pattern exhibited three diffraction lines withd-spacings at 43.2, 24.9, and 21.6 Å and corresponding to the (100),(110) and (200) reflections, respectively, of a hexagonal mesostructure.The ²⁷Al-NMR spectrum for this particular sample is shown in FIG. 1. Inagreement with the findings reported by Corma and his coworkers, theMCM-41 aluminosilicate mesostructure prepared by this procedure hasabout 1/3 of the Al-sites in octahedral coordination and the remainderin tetrahedral coordination after calcination. The tetrahedral Al-sitesexhibited a chemical shift at 53 ppm relative to 1.0 M aluminum nitratesolution, whereas the chemical shift for the aluminum in octahedralsites was 0 to 10 ppm. These chemical shifts are in agreement with thetypical literature values (i.e. 53˜56 ppm for tetrahedral aluminum and˜0.0 ppm for octahedral aluminum for a conventional Al-MCM-41.

EXAMPLES 2 TO 3

[0186] These two Examples illustrate according to the teachings of thepresent invention the preparation of protozeolitic aluminosilicateprecursors (zeolite seeds) that are useful for the supramolecularassembly of hexagonal, cubic, lamellar, wormhole, and cellular foamframework structures that are steam-stable in comparison to likestructured compositions obtained from conventional aluminosilicateprecursors. The preferred aluminosilicate precursors of this inventioncontain nanosized aluminosilicate clusters in which the aluminum is intetrahedral coordination and linked through bridging oxygen atoms tosilicon tetrahedra that in are largely connected to other tetrahedra.These nanosized aluminosilicate precursors are capable of promoting thecrystallization of atomically ordered zeolite phases when mixed withsuitable gels and aged under hydrothermal conditions. Owing to theirability to nucleate zeolitic phases, such as zeolites type Y (moreprecisely faujasitic zeolites) and ZSM-5 (more precisely MFI zeolites),these highly cross-linked precursors are often referred to as “zeoliteseeds”. Therefore, the aluminosilicate precursor of Example 2 isreferred to here as a “zeolite type Y seeds” composition, because it isknown to promote the crystallization of Type Y zeolite. Likewise, thecross-linked aluminosilicate precursor of Example 3 is referred to hereas “ZSM-5 seeds”, because the precursor is known to nucleate thecrystallization of ZSM-5 zeolite. However, these zeolite seeds can beused as precursors to mesoporous molecular sieve aluminosilicates withatomically disordered (amorphous) walls, but with a hexagonal, cubic,wormhole, lamellar and cellular framework structures that aresufficiently order on a mesoscopic length scale to exhibit correlationpeaks in the powder X-ray diffraction pattern and transmission electronmicroscopy (TEM) images indicative of the said framework structures.

[0187] The type Y zeolite seeds composition of Example 2, whichcontained 10 mole % aluminum (Si/Al=9/1), was prepared in the followingmanner. A NaOH aqueous solution with 0.088 mole NaOH and 8.5 mole H₂Owas prepared and 0.10 mole NaAlO₂ was added to this NaOH solution understirring until a clear solution formed. To this basic sodium aluminatesolution was added 1.0 mole of sodium silicate from a 27 wt % sodiumsilicate solution under vigorous stirring until a homogeneousopalescence gel formed. To obtain the Y-seeds composition, the gel wassequentially aged at ambient temperature over night and then at 100° C.over night.

[0188] Example 3 describes the preparation of a solution of ZeoliteZSM-5 seeds containing 1.5 mole % aluminum according to the generalmethod described by deMoor et al., J. Phys. Chem. B 103 1639 (1999). Areaction mixture containing 6.7 mmole of tetrapropylammonium ions as thezeolite seeds director (6.7 mL of 1.0 M tetrapropylammonium hydroxide),0.50 mmole sodium aluminate (Strem Chemical) and 33.3 mmole fumed silica(Aldrich Chemical) in 1270 mmole of water was aged with stirring at 50°C. for 18 hr to form the seeds.

[0189]²⁷Al-MAS NMR spectra of the protozeolitic seeds compositions wererecorded on a Varian VRX 400S instrument in a zirconia rotor at spinningspeeds of 2 kHz and 900 Hz, respectively. The spectra are shown in FIG.2. FIG. 2A provides the X-ray diffraction pattern of the 10% Al-Y-seedsobtained by smearing the Y-seeds gel on a glass plate in the absence(bottom) or the presence of ethanol (top) to help promote theaggregation of the aluminosilicate precursor. The single ²⁷Al NMR lineswith chemical shifts of 55 and 59 ppm correspond to aluminum in azeolite-like tetrahedral environment. In other words, thealuminosilicate species in the precursor compositions exhibit an ²⁷AlNMR pattern consistent with the presence of nano-sized aluminosilicateclusters, as reported in the literature for typical zeolite seeds (Whiteet al, J. Chem. Soc., Faraday Trans. 1998, 94, 2181; van Santen et al,J. Phys. Chem. 1999, 103, 1639).

[0190] Several of the following examples will illustrate the use of thenano-clustered zeolite seeds of Examples 2 and 3, as well as otherzeolite seeds, as precursors for the assembly of aluminosilicatemesostructures with hexagonal, cubic, wormhole and cellular foamframeworks that are ultrastable under steaming conditions in comparisonto mesoporous aluminosilicate molecular sieves prepared fromconventional precursor solutions.

EXAMPLES 4 TO 6

[0191] These three Examples were designed to illustrate the use ofnanoclustered zeolite Y seeds according to art of the present inventionfor the preparation of steam-stable mesoporous aluminosilicate molecularsieves with long range hexagonal order (denoted hexagonal Al-MSU-S fromzeolite Y seeds) even at high tetrahedral aluminum concentrations in theframework. The hexagonal order is retained even after the mesostructureshave been calcined to remove the surfactant. These mesostructures, asformed from zeolite Y seeds, also exhibited a ²⁷Al-NMR resonance with achemical shift substantially greater than 56 ppm, indicating a zeolitictype Y connectivity of SiO₄ and AlO₄ units in the framework walls. Thisminimum chemical shift value for our new aluminate mesostructures asformed from zeolite Y seeds is larger than the previously reportedliterature values for all known aluminated derivatives of silicamesostructures, regardless of the long range structural order of themesostructure or the method used to form the aluminated derivatives.Moreover, the aluminum NMR chemical shifts for our new aluminosilicatemesostructures formed from zeolite Y seeds are comparable to the valuestypically observed for the siting of aluminum centers steam stablezeolite Y itself.

[0192] These examples also illustrate how the use of zeolite type Yseeds in the present invention overcomes the structural disorderingeffect of direct aluminum incorporation that is normally encounteredwhen conventional aluminosilicate precursors are used in the assembly ofa mesoporous aluminosilicate with intended long range hexagonal order.The three mesoporous aluminosilicate molecular sieves of Examples 4, 5,and 6 have Al-loading of 2 mol %, 10 mol % and 20 mol %, and are denoted2%Al-, 10%Al., And 20%Al-MSU-S_(H), respectively. The molar compositionsof the reaction mixtures used to prepare the steam-stable compositionsof these examples were as follows:

[0193] 0.02, 0.10, or 0.20 mole NaAlO₂, corresponding to thecompositions of Examples 4, 5, and 6, respectively.

[0194] 0.088 mole NaOH

[0195] 1.0 mole sodium silicate

[0196] 0.25 mole CTAB surfactant

[0197] 0.62 mole H₂SO₄

[0198] 130 mole H₂O

[0199] Gel-like type Y zeolite aluminosilicate seeds with the desiredaluminum content were prepared according to the general method ofExample 2 and diluted with 127 moles of water. To the diluted mixture,was added sequentially 0.044 mole H₂SO₄ and 0.20 mole CTAB understirring at room temperature for 30 minutes. The resultant mixture wasfurther acidified with 0.48 mole H₂SO₄ and aged at 100° C. for 20 h. Themixture then was acidified with 0.098 mole H₂SO₄ under vigorous stirringand aged at 100° C. again for 20 h to obtain the as-made aluminosilicatemesostructure. The as-made mesostructure was exchanged with 0.1 M NH₄NO₃solution, dried at room temperature, and calcined at 540° C. for 7 h toremove the surfactant.

[0200]FIG. 3 shows the powder X-ray diffraction patterns for thecalcined form of hexagonal 20%Al-MSU-S from zeolite Y seeds (Example 6).The four well-expressed reflections were indexed to the (100), (110),(200) and (210) reflections of a hexagonal mesophase. The calcinedhexagonal 2%Al- and 10%Al-MSU-S mesostructures exhibited equivalentdiffraction patterns. Equally important, each of calcined mesostructuresexhibited a ²⁷Al MAS NMR chemical shift at about ˜62 ppm which iscomparable to the shift of steam stable Y zeolites (FIG. 4). The BETsurface area (m²/g) and pore volumes (cc/g) of the mesostructuresprepared in Example 4 to 6 were 1037 and 0.80, 978 and 0.70 and 599 and0.51, respectively. In each case, the average Horvath-Kawazoe pore sizedetermined from the nitrogen adsorption isotherm was about 3.3 nm.

EXAMPLE 7

[0201] This example illustrates that our new aluminosilicate mesoporousmolecular sieves, as prepared from zeolite type Y seeds according toExamples 4 to 6, is not limited to cetyltrimethylammonium ions as thestructure director and that they can be formed using other quaternaryammonium ion surfactants, as well. In this example,tetradecyltrimethylammonium bromide (TTAB) was used in place of CTAB asthe structure director. A reaction mixture containing 0.25 mole TTAB asthe surfactant structure director and a 20 mol % Al type Y zeolitealuminosilicate precursor was prepared and processed in the same way asdescribed in Examples 4 to 6. The resultant calcined product exhibited awell-expressed hexagonal X-ray diffraction pattern with a basal spacingof 37.0, 21.3, 18.5 and 14.0 A, corresponding to the (100), (110), (200)and (210) reflections of a hexagonal mesostructure, respectively. Themagic angle spinning ²⁷Al-NMR spectrum for the calcined sample exhibiteda resonance with a chemical shift of 62 ppm.

EXAMPLES 8 TO 10

[0202] These Examples 8 and 9 were designed to demonstrate the art ofthe present invention for the preparation of our new aluminosilicatemesostructures with long range cubic order, which we denote cubicAl-MSU-S from zeolite Y seeds. These cubic compositions also exhibittetrahedral ²⁷Al-NMR resonances at chemical shifts greater than 56 ppmand similar to the chemical shift of HY zeolite. Two cubic mesoporousaluminosilicate molecular sieves with Al contents of 2 mol %, and 10 mol% were prepared corresponding to Examples 8 and 9, respectively.

[0203] To obtain the said cubic mesostructures, gel-like zeolite type Yaluminosilicate seed precursors with the appropriate Al content wereobtained according to Example 2 and diluted with 127 mole water. Foreach mole of silicon used in the reaction mixture, the diluted gel wasfirst treated with 0.044 mole H₂SO₄ to lower the pH. Then 0.12 mole CTABand 3.0 mole ethanol as a co-surfactant was sequentially added undervigorous stirring at ambient temperature. After being stirred for 40minutes the pH of the reaction mixture was reduced with the addition of0.14 mole H₂SO₄. The resulting mixture was transferred to a Teflon-linedautoclave and aged at 150° C. for 15 h. The as-made products wererecovered by filtration, air-dried and then calcined at 540° C. for 7 hto remove the surfactant.

[0204] In FIG. 5, the top diffraction pattern is for the calcined10%Al-MSU-S sample prepared from type Y zeolite seeds as described inExample 9. The bottom diffraction pattern is for 2%Al-MCM-48 as acontrast sample (Example 10). This contrast sample was prepared fromconventional precursors by mixing diluted sodium silicate (1.0 mole) andsodium aluminate (0.02 mole) and NaOH (0.088 mole) solutions to obtain aclear solution and then reducing the pH immediately with 0.18 moleH₂SO₄. Then, 0.12 mole CTAB and 3 mole ethanol per mole of silicon wassequentially added under vigorously stirring at ambient temperaturebefore transferring the reaction mixture to a Teflon-lined autoclave toage at 150° C. for 15 h. The product was then washed and calcined at540° C. to remove the surfactant. This same procedure afforded awell-ordered cubic MCM-48-like silica when the aluminum was omitted fromthe reaction mixture.

[0205] It is clear from the XRD pattern for the calcined cubic10%Al-MSU-S mesostructure in FIG. 5 that a well ordered cubic mesoporousaluminosilicate molecular sieves was obtained from type Y zeolite seedsas the inorganic precursor. In contrast, FIG. 5 also shows that thecalcined 2%Al-MCM-48 mesostructure prepared from conventional sodiumaluminate, sodium silicate precursors and surfactant is disordered asjudged from the broad low angle x-ray reflections.

[0206] The ²⁷Al-NMR spectra of 2%Al-MSU-S from Example 8 and 2%Al-MCM-48from Example 10 are shown in FIG. 6. The zeolite-like resonance at achemical shift of 62 ppm clearly indicates the exclusive presence oftetrahedral Al-sites for the cubic 2%Al-MSU-S. An analogous result wasobtained for the cubic 10%-MSU-S mesostructure prepared in Example 9.However, the resonance for the tetrahedra aluminum in 2%Al-MCM-48 occursat a chemical shift of 56 ppm. In addition, this latter mesostructureexhibits a resonance (indicated by the arrow) at 0 ppm corresponding tooctahedral Al-sites. Consequently, we can conclude that pre-formation ofprotozeolitic (type Y zeolite) aluminosilicate nanoclusters indeedimproves the long range order of cubic mesostructures as well as theAl-siting in these mesoporous molecular sieves. The BET surface area(and pore volume) measured from N₂ adsorption isotherms for the MSU-Ssamples prepared from Example 8 and 9 were 976 (0.70) and 599 m²/g (0.51cc/g). The effective pore size calculated from the Horvath-Kawazoe modelwas 2.6 nm for both samples.

EXAMPLES 11 AND 12

[0207] These two examples were designed to illustrate the versatility ofusing pre-formed zeolite type Y and zeolite ZSM-5 aluminosilicatenanoclusters to assemble mesoporous molecular sieves with a wormholeframework structure, denoted wormhole Al-MSU-S from type Y zeolite seedsand ZSM-5 zeolite seeds, respectively, with zeolite-like tetrahedralAl-sites (as judged from ²⁷Al NMR chemical shifts), as well as texturalporosity that is useful for catalysis.

[0208] Example 11 made use of preformed Zeolite Y (faujasitic) seedsprepared as described in Example 2. Example 12 made use of preformedZSM-5 seeds as described in Example 3. In Example 11 a 10%Al-containingseeds composition was prepared as described in Example 2 and then 0.073mole CTAB was added per mole of Si under vigorously stirring at ambienttemperature for 30 minutes. The resultant mixture was aged at 100° C.for 2 days and the product was filtered, washed and air-dried.

[0209] For Example 12, a clear 1.5%Al-ZSM-5 seeds solution obtained asdescribed according to the general procedure of Example 3 and then 5.50mmole CTAB and 1000 mmole water was added at ambient temperature understirring. The resultant mixture was aged at 100° C. for 2 days and theproduct was recovered by filtration, washed and air-dried. Thesurfactant in the samples obtained from Examples 11 and 12 was removedfrom the framework pores by calcination at 540° C. in air for 7 h.

[0210]FIGS. 7A and 7B show the TEM images obtained for the wormholeMSU-S samples prepared in examples 11. A similar image was obtained forthe product of Example 12. The images were recorded on a JEOL 100CXinstrument with an electron beam accelerated at 120 kV using CeB₆ gun.The samples were dusted onto a copper-grid to obtain the images. Bothwormhole-like framework pore channels and intraparticle texturalmesopores are observed for both samples. The textural pores result fromthe intergrowth of nanoscale framework domains of primary particles. Inagreement with the textural porosity evident in the TEM images, the N₂adsorption-desorption isotherms, as shown in FIG. 8 for the product ofExample 11 exhibits a large amount of textural porosity as evidenced bythe hysteresis loop at partial pressures above 0.80. A similar isothermwas obtained for the calcined product of Example 12. The filling of theframework wormhole pores is indicated by the step in the adsorptionisotherms at partial pressures between 0.25 and 0.45. In agreement witha wormhole framework structure, the X-ray diffraction patterns (FIG. 9)for the calcined aluminosilicate mesoporous molecular sieve of Example11 contained a single intense X-ray diffraction line corresponding tothe correlation length between the wormhole pores and a weak higherorder refection at higher scattering angle. A similar XRD pattern wasobtained for the calcined product of Example 12. Also, the ²⁷Al-NMRspectra for the wormhole mesostructure assembled from type Y zeoliteseeds exhibited a zeolitic chemical shift at ˜61 ppm, in accord with theshifts observed for the samples prepared in Example 4 to 6.

EXAMPLE 13

[0211] The purpose for this example was to show that the hexagonalaluminosilicate mesostructures prepared from nanoclustered zeolite typeY seeds according to the present invention are capable of survivingexposure to steam at 800° C., at least when the structures are free ofsodium ions and surfactant.

[0212] Samples of hexagonal 10%Al-MSU-S and 20%Al-MSU-S, were preparedfrom nanoclustered zeolite Y type seeds according to the generalprocedure described in Examples 4 to 6. One-gram quantities of eachas-made sample were separately treated with 100 ml 0.1 M NH₄NO₃ aqueoussolution at 100° C. for overnight. The treated samples were recovered byfiltration and calcined at 540° C. in air for 7 hours to remove thesurfactant in the mesopores. These calcined samples were used for steamstability testing. Each sample was steamed at 800° C. for 5 hours in thea stream of 20 vol % steam-containing N₂. Then the X-ray diffractionpatterns and nitrogen adsorption isotherms were used to investigate theretention of a mesoporous structure after steaming.

[0213] The apparatus 10 used to steam the samples of this example, aswell as the samples of all subsequent examples, is illustrated in FIG.31 and FIG. 31A. A stream of nitrogen at atmospheric pressure (˜20 ccper min) was passed through a flask of water heated at 62±1° C. at avapor pressure of 156 torr. A syringe needle was used to produce finenitrogen bubbles saturated by the water vapor. The sample chamber designensures the uniform passage of the steam through the sample.

[0214] As shown in FIG. 10, it is obvious that the aluminosilicatemesostructures formed from preformed aluminosilicate nanoclustersretained their hexagonal structural integrity entirely, but theconventional MCM-41 like hexagonal mesostructure collapsed aftersteaming treatment at 800° C. for 5 hours. This is in agreement withwhat has been reported previously by Ryoo and his co-workers (Ryoo, J.Phys. Chem. 1995, 99, 16742) regarding the stability of MCM-41 preparedfrom conventional precursors.

[0215] Chemical analysis of the calcined samples before steamingindicated the presence of about 0.8% carbon. Samples calcined forperiods longer or shorter periods than eight hours contained quantitiesof carbon lower than or greater than the 0.8 wt % value, respectively.Also, the degree to which the samples retained a hexagonal X-ray patternand a framework mesoporosity after steaming generally paralleled thecarbon content. Thus, we conclude that the framework embedded carbon, aswell as the zeolite-like connectivity of the framework walls is helpfulin contributing to the steam stability of these materials.

COMPARATIVE EXAMPLE 14

[0216] The purpose of this Example was to prepare a so-calledultrastable 14% Al-MCM-41 mesostructure according to the preparation artof R. Mokaya, as described in Angew.Chem.Int.Ed. 1999, 38 No.19, 2930. A1.0 g calcined sample of a “secondary” MCM-41 silica was preparedaccording to the methodology of Mokaya (see below). To this secondarysilica was added 50 ml of aluminum chlorohydrate (ACH) solution (0.48 Mwith respect to Al) and the mixture was stirred at 80° C. for 2 h. Theresulting solid was collected by filtration and washed with 100 mldistilled water until it was free of Cl⁻ ions, dried at roomtemperature, and calcined in air at 550° C. for 4 h.

[0217] In accord with the teachings of Mokaya, in order to prepare a“secondary” MCM-41 silica, we first prepared a “primary” MCM-41 silica.To obtain the primary MCM-41 silica, 2.0 g of fumed silica was added toa solution containing 3.0 g cetyltrimethylammonium bromide (CTAB) and0.610 g tetramethyl-ammonium hydroxide (TMAOH) in 24 g H₂O at 35° C.under stirring for 1 h. After further stirring for 1 h, the resultingsynthetic gel of molar composition 1.0 SiO₂; 0.25 CTAB: 0.2TMAOH; 40H₂Owas left to age 20 h at room temperature then the mixture wastransferred to a Teflon-lined autoclave and heated at 150° C. for 48 h.The solid product was obtained by filtration, washed with distilledwater, dried in air at room temperature and calcined at 550° C. for 8 h.The “secondary” MCM-41 silica was then prepared from the primary MCM-41silica. To prepare the secondary MCM-41, a synthesis gel of the samemolar ratio was prepared, except that the primary calcined MCM-41 wasused as silica source instead of fumed silica. The synthetic procedureswere identical to the described for the primary synthesis.

[0218] The procedure for the steam stability test was as follows: 0.2 gof ultra stable MCM-41 was put into a Y-shaped quartz tube reactor and astream of 20 vol % water vapor (steam) in N₂ at atmospheric pressure wasintroduced at 800° C. for 5 hours. The 20% water steam in N₂ wasgenerated by passing the nitrogen stream through a saturator chargedwith liquid water at 62° C.±1. The vapor pressure of water at thistemperature is 156 torr. The X-ray diffraction patterns and N₂-sorptionand desorption isotherms were used to evaluate the residual structureafter steaming.

[0219] As shown by the X-ray and N₂ adsorption data in FIGS. 11A, 11Band 11C, the ultrastable 14% Al-MCM-41 of Mokaya underwent structuralcollapse after the steaming treatment at 800° C. for 5 hr. The surfacearea was reduced by 92% (from 760 to 62 m²/g) and the framework porevolume, as determined at a nitrogen partial pressure of 0.96, wasreduced by 88% (from 0.58 to 0.07 cc/g by steaming. Also, the ²⁷Al MASNMR spectrum in FIG. 11 shows that only about half the aluminum is intetrahedral environments (˜51 ppm) and the other half is in octahedralenvironments (˜0 ppm). We conclude that this material lacks the desiredhydrothermal stability for many practical applications in catalysis,especially catalytic cracking of petroleum.

COMPARATIVE EXAMPLES 15 AND 16

[0220] Example 15 describes the synthesis and properties of a typicalhexagonal aluminosilicate mesostructure., hexagonal 10% Al-MSU-S(Si:Al=9:1), derived from seeds that normally nucleate thecrystallization of faujasitic zeolite type Y. The procedure used herefor forming the zeolite type Y seeds follows the general methodologydescribed in the literature (Robson, H. ACS Symp. Ser. 398 436 (1989);and Lechert, L., et al., Stud. Surf. Sci. Catal. 84 147 (1994)).

[0221] Example 16 describes the preparation of a 10%Al-MCM-41 fromconventional silicate and aluminate precursors. The procedure used toform 10% Al-MCM-41 in Example 16 was equivalent to the procedure used inExample 15, except that we eliminated the zeolite seeds-forming stepused in the preparation of the 10% Al-MSU-S in Example 15. We thencompare on the basis of XRD and nitrogen adsorption properties the steamstabilities of these two mesostructures. In addition, we include in thecomparison of steam stability the “ultrastable” Al-MCM-41 prepared asdescribed in Example 14 using the method of Mokaya.

[0222] The hexagonal 10% Al-MSU-S of Example 15 was prepared fromzeolite Y seeds as follows. First, 0.269 g NaAlO₂ was dissolved in asolution of 0.116 g of NaOH in 5.0 ml water to obtain a clear solution.To this solution was added 7.29 g of sodium silicate solution (27 wt %SiO₂, 14 wt % NaOH) under vigorous stirring to obtain a homogeneousmixture. To generate faujasitic type Y zeolite seeds, the resultingmixture was aged at room temperature overnight and then an additional 24hour period at 100° C. under static conditions. The mixture of zeoliteseeds was diluted with 75 ml of water to obtain a milky suspension.Concentrated sulfuric acid (0.142 g) was added to the seeds mixture,followed by the addition of 2.45 g of cetyltrimethylammonium bromide(CTAB) under vigorous stirring for 30 minutes. Then an additional 0.781g of sulfuric acid was added and the mixture was allowed to age at 100°C. under static conditions overnight. Following this aging step anadditional increment of 0.156 g of sulfuric acid were added and themixture was again allowed to age at 100° C. overnight under staticconditions to form the mesostructure. At this point the pH of thereaction mixture was about 9.0 The resulting 10% Al-MSU-S productprepared from zeolite seed precursors was filtered, washed, and dried atambient temperature in air. A 1.0-g quantity of the air-dried productwas treated with 100 ml of 1.0M NH₄NO₃ at 100° C. overnight to displacesodium ions and about half of the surfactant from the mesopores, driedin air, and then calcined at 540° C. for 7 h to remove remainingsurfactant and to convert charge-balancing ammonium ions to protons.Chemical analysis of the calcined product indicated a Si:Al molar ratioof 9:1, along with the presence of 0.80 wt % carbon. We attribute theformation of carbon to the cracking of surfactant in the very acidicmesopores of the zeolite-like framework of the hexagonal Al-MSU-Smesostructure during calcination.

[0223] The disordered hexagonal 10%Al-MCM-41 comparative sample ofExample 16 was prepared from conventional aluminosilicate precursor asfollows. A mixture of 0.269 g of NaAlO₂ and 7.29 g of sodium silicate(27 wt % SiO₂, 14 wt % NaOH) were stirred vigorously to form ahomogeneous mixture and then 75 ml of water was added to form a milkysuspension. To the milky suspension was added sequentially with stirring0.142 g of concentrated sulfuric acid, 2.45 g of cetyltrimethylammoniumbromide with vigorous stirring for 30 minutes, and 0.781 g concentratedsulfuric acid. The resulting mixture was allowed to age overnight at100° C. under static conditions for 1 day. Then 0.156 g of sulfuric acidwas added and the mixture was aged another day at 100° C. The resulting10%Al-MCM-41 mesostructure prepared from conventional aluminate andsilicate precursors was filtered, and dried in air at ambienttemperature. A 1.0-g quantity of the air-dried product was treated with100 ml of 1.0M NH₄NO₃ at 100° C. overnight to displace sodium ions andsome of the surfactant from the mesopores, dried in air, and thencalcined at 540° C. for 7 h to remove remaining surfactant and toconvert charge-balancing ammonium ions to protons. Chemical analysisindicated a Si/Al ratio of 9/1, but the presence of less than 0.04%carbon.

[0224]FIGS. 12A and 12B illustrate the XRD patterns of the followingcalcined aluminosilicate mesostructures before and after steaming in 20%steam at 800° C. for 5 hr: 10% Al-MSU-S from zeolite Y seeds (Example15), 10% Al-MCM-41 from conventional precursor (Example 16). Included inFIGS. 12A and 12B are the corresponding patterns for 14%Al-MCM-41prepared as described in Example 14 using the very recently reportedpost-synthesis grafting reaction between a sodium-free MCM-41 silica andAl₁₃ oligocations (R. Mokaya, Angew. Chem. Int. Ed., 38, 2930 (1999)).This latter grafted form of Al-MCM-41 has been described as beinghydrothermally “ultrastable” in comparison to all previously reportedAl-MCM-41 derivatives. The XRD patterns of calcined 10% Al-MSU-S andultrastable 14%Al-MCM-41 prior to steaming show well expressed hkldiffraction lines indicative of a hexagonal mesostructure. Thediffraction lines for 10%Al MCM-41, made by the direct synthesis routeof Example 16, are substantially broadened. This broadening of thediffraction lines is indicative of the disorder that normallyaccompanies the direct assembly of Al-MCM-41 from conventional aluminateand silicate precursors, particularly when the intended level of siliconsubstitution by aluminum in the framework is greater than about 8 mole%.

[0225] The XRD patterns in FIG. 12B clearly indicate that the10%Al-MSU-S mesostructure assembled from nanoclustered zeolite seedsretains a well ordered hexagonal structure upon steaming at 800° C. Incomparison, the Al-MCM-41 mesostructures prepared both by directassembly from conventional silicate and aluminate precursors and by socalled ultrastable grafting reaction are almost totally destroyed bysteaming. These observations are supported by a comparison of the N₂sorption isotherms shown in FIGS. 13A and 13B for the same series ofmesostructures. The surface areas, framework pore sizes, and porevolumes derived from these sorption isotherms are provided in Table 1.Included in the table are the hexagonal unit cell parameters obtainedfrom the XRD patterns of the samples. Values in parenthesis in Table 1report the percent retention of the surface area and framework porevolume values after steaming in comparison to the values beforesteaming. TABLE 1 Textural properties of calcined mesoporousaluminosilicate molecular sieves before and after steaming in 20% steamin nitrogen at 800° C. for 5 hours. Unit Cell Dimension, a_(o) SurfaceArea Pore Vol. Pore Sample (Å) (m²/g) (cc/g) Dia. (Å) 10% Al-MSU-S(Example 15); Before Steaming 48.6 713 0.56 32.1 After Steaming 44.5 652(91%) 0.42 (75%) 30.3 14% Al-MCM-41 (Example 14): Before Steaming 49.6760 0.58 29.8 After Steaming —  62 (8%) 0.07 (12%) 10% Al-MCM-41(Example 16): Before Steaming 45.5 721 0.53 33.4 After Steaming —  31(4%) 0.03 (6%) —

[0226] The 10% Al-MSU-S sample of Example 15 retains more than 90% ofits surface area and about 75% of its framework pore volume aftersteaming. In addition, the steam treatment improves the texturalporosity of the mesostructure as evidenced by the hysteresis behavior atpartial pressures above 0.50. In contrast, little or no surface area orframework pore volume is retained after steaming for either of the twoAl-MCM-41 samples prepared according to Examples 14 and 16.

[0227] The unique hydrothermal stability of 10% Al-MSU-S from zeolite Yseeds is attributed in part to the retention of a zeolite-likeconnectivity of AlO₄ and SiO₄ tetrahedra upon assembling the zeoliteseeds into a mesostructure. Also, the occluded carbon plays a role incontributing to the structural stability, because samples that arecalcined for longer times at 541° C. or at higher temperatures to removemore carbon exhibited a somewhat larger loss in surface area and porevolume upon steaming. However, in support of the importance of azeolite-like connectivity of SiO₄ and AlO₄ units in the framework walls,the ²⁷Al chemical shift of tetrahedral aluminum in as-made and calcinedAl-MSU-S_(H) occurs at δ=60 ppm, the same value as the seeds solutionand within the 59-65 ppm range observed for most zeolites (Lippma, E.,et al., J. Am. Chem. Soc. 108 1730 (1986)). This chemical shift value isunique among aluminosilicate mesostructures. All previously reportedmesostructured aluminosilicates, including the Al-MCM-41 samples of thepresent work, exhibit a chemical shift of 53-56 ppm. On the basis of therelationship between ²⁷Al chemical shift and the mean bond angle inframework aluminosilicates provided by Lippma et al. (J. Am. Chem. Soc.,108, 1730 (1986)), the mean Al—O—Si angle is substantially smaller (by−8 degrees) for the 10%Al-MSU-S_(H) of Example 15 than for the twoAl-MCM-41 prepared as described in Examples 14 and 16.

EXAMPLE 17

[0228] The acidic properties of hexagonal 10% Al-MSU-S, prepared fromzeolite Y seeds according to the procedure described in Example 15, forcumene cracking over the temperature range 300-450° C. are compared inFIG. 14 with those of 10% Al-MCM-41 assembled according to Example 16from conventional aluminate and silicate precursors. Although the twocalcined mesostructures are nearly equivalent in activity, 10% Al-MSU-Sis a far more active catalyst after exposure to steam. This resultillustrates the potential importance of nanoclustered zeolite seeds asprecursors for the design of hydrothermally stable mesostructures forcatalytic applications.

[0229] The use of zeolite seeds as precursors for the assembly of steamstabile aluminosilicates mesostructures is not limited to compositionscontaining 10 mol % aluminum. Using the general methodology of thisexample, we also have used zeolite Y seeds to prepare hexagonal Al-MSU-Scompositions containing 38 mol % Al with retention of the structural,steam stability, and acidic properties found for 10% Al-MSU-S. Inaddition, the approach is not limited to the use of type Y zeoliteseeds, as illustrated in the following example.

EXAMPLE 18

[0230] Example 18 utilizes ZSM-5 (also known as MFI-type) zeolite seedstemplated by tetrapropylammonium ions to form a hexagonal 2%Al-MSU-Saluminosilicate molecular sieve with superior hydrothermal stability. Incontrast to the Al-MSU-S compositions reported in Examples 4, 5, 6, and8 where the ²⁷Al MAS NMR chemical shifts are well within the zeoliticrange of 57-65 ppm, the ²⁷Al MAS NMR shift observed for the product ofthis example was equivalent to the shift found for the initial ZSM-5seed precursor and comparable to the shifts typically found foraluminosilicate mesostructures assemble from conventional aluminate andsilicate precursors (53-56 ppm). However, the resulting mesostructureshowed an infrared absorption band indicative of the presence of ZSM-5type secondary building blocks in the framework walls. The presence of astable, zeolite-like framework wall structure for the product of thisexample was verified by a hydrothermal stability to both steam andboiling water. Seeds made from TEOS are not as good as those made fromfumed silica.

[0231] Tetraethylorthosilicate (6.83 g) was added with stirring to 7.22ml of 1.0 M tetrapropylammonium hydroxide and then 0.17 g of aluminumsec-butoxide was added to form a clear solution. A 75-ml portion ofwater was added to the stirred solution, and the solution was allowed toage at 85° C. overnight (16 hr) under static conditions to form a clearsolution of ZSM-5 zeolite seeds. A 2.45-g portion ofcetyltrimethylammonium bromide then was added under vigorous stirringfor 30 minutes, and the resulting mixture was allowed to age at 100° C.under static conditions overnight (16 h). The pH of the reaction mixturewas lowered to a value of 9.0 by the addition of 1.0 M sulfuric acid andthe reaction mixture was aged again overnight at 100° C. under staticconditions. The mesostructured precipitate was filtered, washed, driedin air and then calcined at 550° C. to remove the surfactant. The X-raypowder diffraction pattern of the calcined 2%Al-MSU-S product exhibitedfour diffraction lines (100, 110, 200, 210) consistent with a hexagonalmesostructure. The ²⁷Al MAS NMR spectrum of the calcined productexhibited a single resonance line at 55 ppm, consistent with the samelinked AlO₄ tetrahedral environment as in ZSM-5 seeds (see the ²⁷Al MASNMR spectrum for ZSM-5 seeds in FIG. 2).

[0232] Further evidence for a protozeolitic framework wall structure wasobtained from the infrared absorption spectrum of the calcined2%Al-MSU-S mesostructure. As shown in FIG. 15, absorption bands between500 and 600 cm⁻¹, consistent with the presence of secondary 5-memberedring sub-units, are observed. Secondary 5-membered ring sub-units are acharacteristic feature of crystalline pentasil zeolites, a family ofzeolites that includes ZSM-5 zeolite. Thus, we conclude that the wallsof the mesostructure contain the sub-units of a pentasil zeolite, eventhough the walls lack the atomic crystallinity of a zeolite. Included inFIG. 15 for comparison purposes are the infrared spectra for anauthentic sample of 2%Al-ZSM-5 zeolite and for a disordered hexagonal5%Al-MCM-41 assembled from conventional aluminate and silicateprecursors. The same bands between 500-600 cm⁻¹ were found for the ZSM-5zeolite, but the 5%Al-MCM-41 made from conventional precursors does notshow these zeolite-like absorption bands.

[0233] Kloetstra et al (Chem. Commun., 2281 (1997)) have reported ahexagonal aluminosilicate mesostructure which on the basis of IR bandsbetween 500 and 600 cm⁻¹ also contains 5-membered ring structuresanalogous to the secondary building blocks of ZSM-5 zeolite. Thismaterial was prepared by exchanging a conventional Al-MCM-41 withtetrapropylammonium ions and subsequently heating the exchangedmesostructure in glycerol to convert some of the framework intoembryonal ZSM-5 units. However, we find upon repeating this work thatthe mesostructure of Kloetstra et al is hydrothermally unstable. Boilingthe material in water for 5 hours or exposing it to 20% steam innitrogen stream at 600° C. for 5 hours results in nearly the completeloss of framework mesoporosity. In contrast, the hexagonal 2%Al-MSU-S ofExample 18 retains nearly all of its framework mesoporosity under theseconditions, Thus, the introduction of ZSM-5 type building blocks intothe framework walls of MCM-41 by the method of Kloetstra appears to belocalized to specific regions of the framework adjacent totetrapropylammonium cations, whereas the use of zeolite seeds asprecursors according to Example 18 affords a more uniform framework ofprotozeolitic connectivity of SiO₄ and AlO₄ units and, hence, greatlyimproved hydrothermal stability.

EXAMPLE 19

[0234] This example demonstrates that preparation of zeolite seeds forthe assembly of hydrothermally stable aluminosilicate mesostructures isnot limited to the use of sodium silicate precursor solutions containing27 wt % SiO₂, 14 wt % NaOH. Sodium silicate solutions containing higherratios of silica to sodium hydroxide are also suitable for forming thezeolite seeds needed for the supramolecular assembly of hydrothermallystable aluminosilicate mesostructures.

[0235] Example 19 illustrates the use of a sodium silicate solutioncontaining 28.43 wt % SiO₂ and 8.93 wt % NaOH for preparing zeolite typeY nucleating centers (seeds) and the subsequent use of these zeoliteseeds for preparing an aluminosilicate mesostructure with a zeolite-like²⁷Al MAS NMR chemical shift in the range 57 to 65 ppm. The method usedto prepare the seeds follows the general procedure provided by Vaughan(U.S. Pat. No. 4,178,352) for a zeolite Y seeds composition containing35 mole % aluminum (Si/Al=1.88). A NaOH aqueous solution containing1.013 mole NaOH and 7.6 mole H₂O was prepared and 0.54 mole NaAlO₂ wasadded to this NaOH solution under stirring until a clear solutionformed. To this basic sodium aluminate solution was added 1.0 mole ofsodium silicate (28.43% SiO₂, 8.93 wt % NaOH, 41 degree, Be′,) in 6.6mol H₂O under vigorous stirring. The product set to a stiff gel within 2minutes after mixing was completed. This gel contains type Y zeoliteseeds or nucleation centers. In order to form a steam-stable mesoporousaluminosilicate the zeolite Y seeds, 127 mol H₂O was added. To thediluted mixture was added sequentially 0.5065 mole H₂SO₄ and 0.20 moleCTAB under stirring at room temperature for 30 minutes. The resultantmixture was further acidified with 0.15 mole H₂SO₄ and aged at 100° C.for 20 h. The mixture then was acidified with 0.029 mole H₂SO₄ undervigorous stirring and aged at 100° C. again for 20 h to obtain theas-made aluminosilicate mesostructure. The as-made mesostructure werewashed thoroughly with water and dried in air. The product was calcinedat 540° C. for 7 h to remove the surfactant. The calcined productexhibited a single XRD line consistent with a wormhole frameworkstructure and denoted wormhole 35%Al-MSU-S from zeolite Y seeds. Thecorresponding XRD basal spacing was about 5.0 nm. The chemical shift forthe calcined product was 59 ppm, within the 57-65 ppm range expected fora hydrothermally stable aluminosilicate mesostructure assembled fromzeolite Y seeds.

EXAMPLE 20

[0236] This example also illustrates the formation of a disorderedaluminosilicate mesostructure from zeolite Beta seeds using TEOS(tetraethylorthosilicate) as the silica source.

[0237] Tetraethylammonium hydroxide (TEAOH) was used as the template forzeolite Beta seeds formation (J. Perez-Pariente, J. A. Martens and P. A.Jacobs, Applied Catalysis, 31, 35, 1998). TEAOH (0.00665 mol) was mixedwith NaAlO₂ (0.0005 mol) in 1.2 mol H₂O under stirring to obtain a clearsolution at ambient temperature. Then TEOS (0.0333 mole) was added toobtain an opaque solution under stirring. The solution was aged at 35°C. for 100 h to produce a cloudy Zeolite Beta seeds solution. To thesolution at 35° C. was added 0.00823 mol CTAB at 35° C. under stirring.The resultant mixture was aged at 100° C. in a Teflon-lined autoclavefor 2 days. The solid product was filtered, washed with hot water anddried at room temperature. The surfactant was removed by calcination at550° C. for 4 h. The XRD exhibited a single diffraction linecorresponding to a spacing of 3.8 nm and a weak shoulder, as expectedfor a wormhole structure or a distorted hexagonal structure.

[0238] The IR spectra of the TEOS-derived Beta zeolite seeds and theresulting mesostructure formed from these seeds exhibited an IR bandnear 550-560 cm⁻1, indicating the presence of 5-membered ring subunits.However, the broadness of the XRD pattern indicated that TEOS is lesspreferred than fumed silica (see Example 21 below) in forming zeoliteBeta seeds for the assembly of aluminosilicate mesostructures withwell-expressed hexagonal framework symmetry. This does not preclude TEOSfrom being generally useful as a precursor for forming zeolite seeds,suitable for the assembly of steam stable zeolites. For instance, themesostructure obtained in this example was stable to 20% steam at 600°C. for 5 hr., retaining at least 88% of the surface areas and frameworkpore volumes observed before steaming.

EXAMPLE 21

[0239] This example illustrates the preferred use of fumed silica forthe preparation of pentasil zeolite seeds and the use of these seeds forthe formation of well ordered aluminosilicate mesostructures that aresteam stable in comparison to aluminosilicate solutions which have notbeen templated by a structure-directing agent for the formation ofzeolite seeds. Although the supramolecular assembly of steam stableMSU-S aluminosilicate mesostructures is quite general and can be formedfrom any protozeolitic aluminosilicate solution, the pentasil zeoliteseeds, especially zeolite ZSM-5 (MFI) and Beta (BEA) seeds, areespecially preferred when formed from fumed silica. As will be shown bythe steam stability tests of this example hexagonal MSU-S mesostructuresformed from these protozeolitic seeds are stable to exposure to 20%steam at 600°-800° C. for substantial periods of time. Also, thesestructures have superior activity for acidic catalysis in comparison tohexagonal aluminosilicate mesostructures formed from conventionalaluminosilicate precursors.

[0240] Aqueous solutions of nanoclustered ZSM-5 and Beta zeolite seeds(Si/Al=67) were prepared using tetrapropylammonium (TPA⁺) andtetraethylammonium (TEA⁺), respectively, as a templates (Camblor, etal., Stud. Surf. Sci. Catal. 105 341 (1997); deMoor et al., J. Phys.Chem. 13 103 1639 (1999)). For comparison purposes, conventionalaluminosilicate anions were prepared using tetramethylammonium ions(TMA⁺) in place of TPA⁺ and TEA⁺. TMA⁺ is not known to function as atemplate for MFI or BEA zeolite seeds.

[0241] An aqueous solution of nanoclustered ZSM-5 seeds (Si/Al=67) wasprepared by the reaction of 1.0 M tetrapropylammonium (TPA⁺) hydroxide(6.7 mmol), sodium aluminate (0.50 mmol, Strem Chemicals, Inc.) andfumed silica (33.3 mmol, Aldrich Chemicals) in water (1270 mmol) at 50°C. for 18 h. The same stoichiometric ratio of tetraethylammonium (TEA⁺)hydroxide, sodium aluminate, fumed silica and water was used to preparea solution of zeolite Beta seeds at 100° C. A conventionalaluminosilicate precursor solution was prepared using the sameexperimental methodology except that TMA⁺ was used in place of TPA⁺ andTEA⁺.

[0242] The evaporation of each of the aluminosilicate solutions affordedpowders with amorphous X-ray diffraction patterns. However, as shown inFIG. 16, the IR spectra of the powdered forms of the MFI and BEA zeoliteseeds revealed distinct vibrations between 500-600 cm⁻¹. In contrast, noIR bands were observed in this range for the conventionalaluminosilicate anions formed when TMA⁺ hydroxide was used in place ofTPA⁺ or TEA⁺ hydroxide. A band near 550 cm⁻¹ in pentasil ZSM-5 and Betazeolites is indicative of the presence of five-membered rings. Thus, thepresence of an analogous band in the case of the TPA⁺ and TEA⁺aluminosilicate precursors verifies the presence of pentasil zeoliteseeds.

[0243] Hexagonal aluminosilicate mesostructures, generally denotedMSU-S_(H) from ZSM seeds and MSU-S_(H) from Beta seeds, were assembledby reaction of the respective zeolite seeds solutions withcetyltrimethylammonium bromide (CTAB) at a surfactant to silica ratio of0.25 at a temperature of 150° C. for 2 days. An equivalent procedure wasused to assemble the conventional TMA⁺ aluminosilicate precursors into adisordered MCM-41 mesostructure. The as-made products were calcined at550° C. to remove surfactant, treated with 0.1M NH₄NO₃ at roomtemperature to displace exchangeable sodium ions, and then calcinedagain at 550° C. to convert NH₄ ⁺ at exchange sites to protons. Chemicalanalysis indicated the absence of occluded carbon and a Si/Al ratio inagreement with the ratio contained in the initial zeolite seeds.

[0244]FIG. 17 illustrates the XRD patterns of calcined 1.5% Al-MSU-Sfrom ZSM-5 seeds) and 1.5% Al-MSU-S from Beta seeds) before and afterexposure to 20% (v/v) water vapor in N₂ at 600 and 800° C. for 5 h. TheXRD results clearly indicate that mesostructures retain hexagonal orderupon steaming. The disordered 1.5% Al-MCM-41 also retained long rangestructural order after exposure to steam at 600° C., but at 800° C. themesostructure was almost completely lost. (XRD patterns not shown). Thedisorder initially associated with the 1.5% Al-MCM-41 sample was notresponsible for the loss of long range order. Even well-orderedAl-MCM-41 samples with four hexagonal hkl reflections exhibit a loss ofmesostructure upon steaming at 800° C.

[0245]FIG. 18 provides the N₂ sorption and adsorption isotherms for thetwo calcined MSU-S mesostructures before and after exposure to 20% steamat 600° C. in comparison are the isotherms for 1.5% Al-MCM-41 formedfrom tetramethylammonium hydroxide (TMAOH), sodium aluminate and fumedsilica. Table 2 lists the surface areas, framework pore sizes, and porevolumes before and after exposure to steam at 600° and 800° C. The 1.5%Al-MSU-S_(H) from ZSM-5 seeds and 1.5% Al-MSU-S_(H) from Beta seedsmesostructures retain more than 95% of their surface areas and more than87% of their framework pore volumes with little or no pore contractionafter exposure to steam at 600° C. In contrast, 1.5% Al-MCM-41 assembledfrom conventional aluminosilicate anions retains only 63% of its surfacearea and 36% of its framework pore volume under equivalent steamingconditions. The MSU-S aluminosilicate mesostructures assembled fromZSM-5 and Beta zeolite seeds retain long range hexagonal order uponexposure to steam at 800° C., as judged by XRD (c.f., FIGS. 17A, 17B).In addition, a substantial fraction of the surface area and frameworkpore volume is retained after exposure to 20% steam at 800° C. As shownby the results presented in Table 2, after an exposure time of 2 h theMSU-S mesostructures experienced minor decreases in surface areas andretain at least 50% of the framework pore volume. After an exposure timeof 5 h at 800° C., the pore volume dropped below 50% of the initialframework pore volume. In contrast, the mesostructured framework of 1.5%Al-MCM-41 is completely lost under these conditions. TABLE 2 Texturaland acid catalytic properties of mesoporous aluminosilicate sievesbefore and after steaming. Unit cell Surface Pore Pore Cumene Dimension,area Vol. dia. conv.^(a) Sample a_(o) (Å) (m²/g) (Cc/g) (Å) (%) 1.5%Al-MSU-S from ZSM-5 seeds Calcined 45.3 1231 1.06 36.8 32.3 Steamed 600°5 h 44.5 1192 0.93 34.7 — Steamed 800° 2 h — 1130 0.62 30.6 — Steamed800° 5 h 36.6  849 0.44 24.3 — 1.5% Al-MSU-S from Beta seeds Calcined47.3 1124 1.06 39.1 31.5 Steamed 600° 5 h 46.7 1065 0.94 38.0 — Steamed800° 2 h — 1050 0.68 35.0 — Steamed 800° 5 h 37.0  885 0.46 26.4 — 1.5%Al-MCM-41^(b) Calcined 46.4 1013 1.08 38.7 11.7 Steamed 600 5 h 35.2 639 0.39 20.1 — Steamed 800 5 h —  55 — — —

[0246] The supramolecular assembly of steam stable MSU-S mesostructuresfrom zeolite ZSM-5 and Beta seeds is not limited to a specific loadingof aluminum in the framework. Pentasil zeolite seeds also can be used toassemble steam stable MSU-S mesostructures with Si/Al ratios in therange ˜300-20. We have found that a MSU-S derivative assembled fromfaujasitic zeolite type Y seeds, denoted hexagonal MSU-S from zeolite Yseeds, retains nearly all of its pore structure after exposure to 20%steam at 800° C. for several hours. Zeolite Y seeds, however, are onlyobtainable at much lower Si/Al ratios (typically in the range ˜2.5-10).Other zeolite seeds, such as Linde Type A (or Type A zeolite) seeds areexpected to provide mesostructures with Si/Al ratios of 1.0. It is wellknown according to Lowenstein's rule that zeolite compositions avoidSi/Al ratios less than 1.0. Ammonium ion exchange of the mesostructuresformed from zeolite Y seeds could be accomplished in the presence of thesurfactant.

[0247] Depending upon calcination conditions to remove the surfactant,the resulting mesostructure assembled from zeolite Y seeds may containoccluded carbon in the framework mesopores. This occluded carbon, whichis presumed to form through cracking of the surfactant duringcalcination, modifies the surface polarity and makes the framework wallsmore resistant to hydrolysis. The as-made mesostructures formed fromZSM-5 and Beta zeolite seeds, however, have the great advantage ofproviding steam-stable compositions with much higher Si/Al ratios(Si/Al˜300-20). Also, mesostructures formed from pentasil zeolite seedscan be calcined to remove the surfactant and subsequently NH₄⁺-exchanged without the loss of long range order or the occlusion ofcarbon. This implies that these mesostructures derived from pentasilzeolite seeds are less acidic in comparison to mesostructures derivedfrom zeolite type Y seeds, and their steam stability is not dependent onthe presence of carbon on the framework walls.

[0248]²⁷Al MAS NMR measurements indicate that more than 90% of thealuminum centers in calcined 1.5% Al-MSU-S and 1.5% Al-MSU-S are intetrahedrally coordinated sites, as judged from the intensity of thetetrahedral resonance near 53 ppm in comparison to a very weakoctahedral resonance near 0 ppm.

[0249] In association with the tetrahedral siting of aluminum, Bronstedacidity was verified by the cumene cracking activity of thesesteam-stable mesostructures. Cumene conversions for calcined forms of1.5% Al-MSU-S from ZSM-5 seeds, 1.5% Al-MSU-S from Beta seeds, and 1.5%Al-MCM-41 at 300° C. are included in Table 2. Clearly, the Al-MSU-Sderivatives are far more active acid catalysts than the Al-MCM-41prepared from conventional aluminosilicate precursors.

[0250] It was concluded on the basis of the above example that thesubstantial improvement in both the hydrothermal stability and catalyticactivity is due to a zeolite-like connectivity of AlO₄ and SiO₄tetrahedra in framework walls of the aluminosilicate mesostructures.Evidence for the retention of a zeolitic seeds structure in theframework walls of calcined MSU-S from ZSM-5 seeds and MSU-S from Betaseeds mesostructures was provided by the retention of the same5-membered ring IR absorption bands found for the initial zeolite seeds.Compare, for example, the IR spectra in FIG. 19 for the calcined 1.5%Al-MSU-S and 1.5% Al-MCM-41 mesostructures with the spectra in FIG. 16for the initial aluminosilicate precursors. The band characteristics offive-membered rings is well-expressed in the spectra of MSU-S from ZSM-5seeds and MSU-S from Beta seeds, but not for the MCM-41 derivative.

[0251] Improvements in the steam stability and acidity foraluminosilicate mesostructures can be anticipated through theincorporation of other families of zeolitic seeds in the frameworkwalls. Future studies can be expected to focus on this very promisingapproach to the supramolecular assembly of steam-stable derivatives.

EXAMPLE 22

[0252] The purpose of this Example was to show that steam stablealuminosilicate mesostructures can be assembled from a mixture ofzeolite Y seeds and conventional sodium silicate as the silica source.The advantage of this methodology is in part that it allows for thepreparation of stable structured aluminosilicate compositions with Si/Alratios greater than or about equal to 10 from a zeolite Y seedscomposition that normally is prepared at Si/Al ratios less than 10. Thestructure directing surfactant used in this example was PLURONIC 123,illustrating further that a non-ionic surfactant can be used in place ofan onium ion surfactant.

[0253] A 15% Al zeolite Y seeds composition (Si/Al 5.67) was preparedaccording to the methodology described in Example 2. To 0.6 ml 0.6M NaOHsolution, 0.00074 mol NaAlO₂ was added under stirring, then 0.0042 molsodium silicate (27% SiO₂, 14% NaOH) was added under vigorous stirringuntil a homogeneous opalescence gel was formed. To obtain the zeolite Yseeds composition, the gel was sequentially aged at ambient temperature(18 hr) and then at 100° C. overnight (20 hr). To the seeds solution wasadded 25 ml H₂O and 0.0328 mol sodium silicate (27% SiO₂, 14% NaOH)under stirring. The resultant mixture contained 2 mol % Al or a Si/Alratio of about 49.

[0254] The surfactant solution was prepared by adding 2.4 g PLURONIC 123to 40 ml H₂O under stirring for 12 hr. The above zeolite seeds solutionwas added to the surfactant solution and the pH of the mixture wasadjusted to a value in the range 5.5˜6.5 (as judged using Hydrion pHindicator paper) by the dropwise addition of 1:10 (vol:vol) H₂SO₄:water.The reaction mixture was stirred at 50° C. for 40 h. The final productwas recovered by filtration, washed with water and air dried. Thesurfactant was removed by calcination at 600° C. for 4 h. A steamstability test of the sample, denoted MSU-S, was performed at 800° C.for 2 h in 20% steam.

[0255]FIG. 20 illustrates the XRD patterns of the calcined MSU-S samplebefore and after steaming. The XRD results clearly indicate that productretains a well ordered hexagonal structure upon steaming at 800° C.

[0256]FIG. 21 shows the N₂-adsorption and desorption isotherm of themesostructure before and after steaming at 800° C., 2 h.

EXAMPLE 23

[0257] The purpose of this Example was to show that a structuredaluminosilicate composition (Si/Al=49) with a framework pore sizegreater than 10 nm can be assembled from a mixture of zeolite Y seedsand conventional sodium silicate in the presence of a non-ionicpolyethylene oxide surfactant (PLURONIC 123) and an alcohol (1-butanol)as a co-surfactant.

[0258] A mixture of zeolite Y seeds and conventional sodium silicatecontaining 2 mole % Al (Si/Al-49) was prepared as described in Example22. The surfactant solution was prepared by adding 2.4 g PLURONIC 123and 2.4 g 1-butanol to 40 ml H₂O under stirring for 12 hours. To thesurfactant solution was added the aluminosilicate solution. The pH ofthe mixture was adjusted to be in the range 5.5˜6.5 by addition of 1:10(vol:vol) H₂SO₄:water. The reaction mixture was stirred at 50° C. for 40h then kept at 100° C. for 20 h under static conditions. The product wasrecovered by filtration, washed and air dried. The surfactant wasremoved by calcination at 600° C. for 4 h.

[0259]FIG. 22 shows the XRD patterns of the calcined product. FIG. 23shows the N₂-adsorption and desorption isotherm of the calcined product.

EXAMPLE 24

[0260] The purpose of this Example was to demonstrate the preparation ofa structured large pore aluminosilicate composition with Si/Al ratio of5.67 from zeolite Y seeds in the presence of a triblock non-ionicsurfactant containing a polypropylene oxide (PPO) and polyethylene oxide(PEO) segments in the sequence PEO-PPO-PEO and in the presence of aco-surfactant (1-dodecanol).

[0261] A zeolite Y seeds composition containing 15 mole % Al wasprepared according to the methodology of Example 2. To 5 ml 0.6 M NaOHsolution, was added 0.0058 mol NaAlO₂ under stirring. Then 0.0328 molsodium silicate (27% SiO₂, 14% NaOH) was added under vigorous stirringuntil a homogeneous opalescence gel was formed. To obtain the finalzeolite seeds composition, the gel was sequentially aged at ambienttemperature and then at 100° overnight. The zeolite Y seeds compositionwas then diluted with 25 ml H₂O.

[0262] A mixture of surfactant and co-surfactant was prepared by adding2.4 g PLURONIC 123 and 2.0 g 1-dodecanol to 40 ml H₂O under stirring.After 12 hours stirring, to the surfactant solution was added thezeolite Y seeds solution. The pH of the mixture was adjusted to a valuein the range 5.5-6.5 (ad judged from Hydrion pH indicator paper) by theaddition of 1:10 (vol:vol) concentrated H₂SO₄:water. The reactionmixture was stirred at 45° C. for 20 h then kept at 100° C. for 2 hstatically. The final product was recovered by filtration, washed andair dried. The surfactant was removed by calcination at 600° C. for 4hr.

[0263]FIG. 24 shows the N₂-adsorption and desorption isotherm of thecalcined product.

EXAMPLE 25

[0264] The purpose of this Example was to show that very large porealuminosilicate compositions with a cellular foam framework structurecan be assembled from a mixture of zeolite seeds and conventional sodiumsilicate precursors.

[0265] Two zeolite seeds solutions containing 2 mole % and 5 mole %aluminum were prepared according to the general method of Example 22from a mixture of zeolite Y seeds (15 mole % Al) and sodium silicate.

[0266] The surfactant solution was prepared by adding 2.4 g PLURONIC 123to 40 ml H₂O under stirring. After 12 hours trimethylbenzene was addedto form an emulsion. To the emulsion, was added one of the above seedssolution (2 mole % aluminum) and the pH value was adjusted to a value inthe range 5.5˜6.5 with 1:10 (vol:vol) concentrated H₂SO₄:water. Ananalogous procedure was used to prepare a second reaction mixture usingthe seeds solution containing 5 mole % aluminum. The reaction mixtureswere stirred at 45° C. for 20 h, then kept under static conditions at100° C. for 20 h. The final product was recovered by filtration, washedand air dried. The surfactant was removed by calcination at 600° C. for4 h.

[0267]FIG. 25 shows the N₂-adsorption and desorption isotherm of thecalcined compositions containing 2% and 5% Al. FIG. 25A shows thecorresponding pore size distributions.

EXAMPLE 26

[0268] The purpose of this Example was to show the assembly of steamstable large pore aluminosilicate compositions with cellular foamframework structures using pentasil zeolite seeds and an emulsion formedfrom a non-ionic polyethylene oxide surfactant (PLURONIC 123) and anaromatic organic co-surfactant (trimethylbenzene) as the structuredirector.

[0269] An aqueous solution of nanoclustered pentasil zeolite ZSM-11seeds (also known as MEL) with a Si/Al ratio of 67) was prepared by thereaction of 40% tetrabutylammonium hydroxide (TBA⁺) solution as theseeds structure director (6.7 mmol), sodium aluminate (0.50 mmol, StremChemicals, Inc) and fumed silica (33.3 mmol, Aldrich Chemicals) in water(2700 mmol) at 130° C. for 3 h.

[0270] The surfactant solution was prepared by adding 2.4 g PLURONIC 123to 30 ml H₂O under stirring. After 12 hours stirring, to the surfactantsolution was added trimethylbenzene to form an emulsion. To the emulsionwas added the above seeds solution and the pH was adjusted to a value of5.5˜6.5 by the addition of 1:10 (vol:vol) concentrated H₂SO₄:water. Thereaction mixture was stirred at 45° C. for 20 hr then kept at 100° C.for 20 h statically. The final product was recovered by filtration,washed and air dried. The surfactant was removed by calcination at 600°C. for 4 h.

[0271]FIG. 26 illustrates the N₂-adsorption and desorption isotherms ofcalcined composition before and after exposure to steam at 650° C. for 4hours and at 800° C. for 2 hours. Note from FIG. 26A that the pore sizeincreased from 20 to 36 and 50 nm upon steaming at 65° and 800° C.,respectively.

EXAMPLE 27

[0272] The purpose of this Example was to show the assembly of steamstable aluminosilicate cellular foam structures from pentasil zeoliteBeta and ZSM-5 seeds.

[0273] Aqueous solutions of nanoclustered aluminosilicate zeolite seeds(Si/Al=50) were prepared by the reaction of 6.7 mmol of 35%tetraethylammonium hydroxide (for preparation of zeolite Beta seeds) ortetrapropylammonium hydroxide (for preparation of ZSM-5 seeds), aluminumtri-sec-butoxide (0.42 mmol, Aldrich Chemicals, Inc.) and TEOS (21.2mmol, Aldrich Chemicals) in water (330 mmol) at 100° C. for 3 h.

[0274] The surfactant solution was prepared by adding 2.4 g PLURONIC 123to 30 ml H₂O under stirring. After 12 hours stirring, to the surfactantsolution was added trimethylbenzene to form an emulsion. To the emulsionwas added the desired seeds solution. The pH of the mixture was adjustedto a value in the range 2˜3 with 37% HCl. The reaction mixture wasstirred at 35° C. for 20 h then kept at 100° C. for 20 h statically. Thefinal product was recovered by filtration, washed and air dried. Thesurfactant was removed by calcination at 600° C. for 4 h.

[0275]FIG. 27 illustrates the N₂-adsorption and desorption isotherms ofthe calcined products before and after exposure to steam at 650° C. for4 hours. Included for comparison is mesoporous cellular foam compositionprepared from conventional precursors as described in Example 28.

COMPARATIVE EXAMPLE 28

[0276] In order to have a contrast example for our newly invented steamstable aluminosilicate compositions with a cellular foam framework, weprepared a mesocellular foam composition containing 2 mole % aluminumaccording to the general preparation art of Stucky and co-workers, asdescribed in J. Am. Chem. Soc. 121: 254 (1999). PLURONIC 123 (2.0 g) wasdissolved in 75 ml of 1.6 M HCl solution at ambient temperature.Trimethylbenzene (2.0 g) was added to form an emulsion. To the emulsionwas added a mixture of TEOS (21 mmol) and aluminum tri-sec-butoxide(0.42 mmol). After aging 20 h at 35° C., the mixture was kept at 100° C.for 24 h. The final product was recovered by filtration, washed and airdried. Surfactant was removed by calcination at 550° C. for 8 h.

[0277] The curves labeled “C” in FIG. 27 illustrate the N₂-adsorptionand desorption isotherm of the calcined product before and afterexposure to steam (650° C., 4 h, 20% H₂O). It is seen that the steamstability of the product of Example 28 is greatly inferior to thestability of the product of Example 27.

[0278] It was also noted that the calcined product of Example 28retained only 23% of its initial surface area after 250 hrs as asuspension (0.10 g/20 cc) in boiling water. In contrast, the calcinedproduct of Example 27 retained 75% of its initial surface area after thesame treatment.

EXAMPLE 29

[0279] The purpose of this Example was to show that an aluminosilicatecomposition with cellular foam framework porosity can be obtained frommixtures of zeolite seeds and sodium silicate as the frameworkprecursors. PLURONIC 123 was used as the non-ionic surfactant and1-dodecanol was the co-surfactant.

[0280] The zeolite seeds solution containing 2% Al was prepared from amixture of zeolite Y seeds and sodium silicate using the methodologydescribed in Example 22.

[0281] The surfactant solution was prepared by adding 2.4 g PLURONIC 123and 2.0 g 1-dodecanol to 40 ml H₂O under stirring. After 12 hoursstirring the above seeds solution was added to the surfactant solution,and the pH was adjusted to a value in the range 5.5˜6.5 with 1:10(vol:vol) concentrated H₂SO₄:water. The reaction mixture was stirred at50° C. for 40 h then kept at 100° C. for 20 h statically. The finalproduct was recovered by filtration, washed and air dried. Thesurfactant was removed by calcination at 600° C. for 4 h.

[0282]FIG. 28 shows the N₂-adsorption and desorption isotherm of thecalcined product and FIG. 28A shows the framework pore sizedistribution.

EXAMPLE 30

[0283] The purpose of this Example was to show that a steam stablestructured aluminosilicate composition with super-microporosity (1.0-2.0nm) and a disordered wormhole framework can be assembled from zeoliteseeds. Decyltrimethylammonium bromide was used as the structuredirecting surfactant.

[0284] Zeolite Y seeds containing 15 mole % Al were prepared accordingto the general method described in Example 2. To 5 ml of 0.6 M NaOHsolution was added 0.0058 mol NaAlO₂ under stirring. Then 0.0328 molsodium silicate (27% SiO₂, 14% NaOH) was added under vigorous stirringuntil a homogeneous opalescence gel was formed. To obtain the desiredzeolite Y seeds composition, the gel was sequentially aged at ambienttemperature (18 hr) and then at 100° C. overnight (20 hr) To the seedssolution was added 75 ml H₂O and 0.0068 mel decyltrimethylammoniumbromide under stirring at ambient temperature for 50 min. The mixturethen was acidified with 0.020 mol H₂SO₄ under vigorous stirring andheated at 100° C. for 40 h. The final product was recovered byfiltration, washed and air dried.

[0285] Treatment of the as-synthesized supermicroporous material with0.1 M NH₄NO₃ at 100° C. displaced exchangeable sodium ions. The productwas calcined at 550° C. for 4 h to remove the surfactant. XRD indicatedthe presence of one diffraction line consistent with a wormholestructure.

[0286]FIG. 29 illustrates the XRD patterns of the disordered calcinedcomposition before and after exposure to 20% steam at 650° C. for 4hours. FIG. 30 is the N₂-adsorption and desorption isotherm of thedisordered calcined composition before and afer exposure to 20% steam at650° C. for 4 hours.

EXAMPLE 31

[0287] The purpose of this example is to illustrate the preparation of acomposite composition comprising a hydrothermally stable hexagonal MSU-Smesostructure and microporous faujasite zeolite crystals from faujasiticzeolite seeds.

[0288] Faujasite zeolite seeds containing 16.7 mole % aluminum(Si/Al=5/1), were prepared in the following manner. A NaOH aqueoussolution with 0.088 mole NaOH and 8.5 mole H₂O was prepared and 0.20mole NaAlO₂ was added to this NaOH solution under stirring until a clearsolution formed. To this basic sodium aluminate solution was added 0.8mole of sodium silicate from a 27 wt % sodium silicate solution undervigorous stirring until a homogeneous opalescent gel formed. To obtainthe faujasite seeds composition, the gel was sequentially aged atambient temperature over night and then at 100° C. over night. Thegel-like faujasite seeds were diluted with 127 moles of water. To thediluted mixture, was added sequentially 0.044 mole H₂SO₄ to decrease thepH and 0.20 mole cetyltrimethylammonium bromide (CTAB) surfactant understirring at room temperature for 30 minutes. The resultant mixture wasfurther acidified with 0.48 mole H₂SO₄ and aged at 100° C. for 48 h toboth crystallize the faujasite zeolite component and the hexagonalmesostructured MSU-S components of the composite composition. Theas-made composite composition was exchanged with 0.1 M NH₄NO₃ solution,air dried and calcined at 550° C. for 4 h.

[0289] The calcined composite composition exhibited an XRD powderdiffraction pattern indicative of a hexagonal MSU-S mesostructure withdiffraction peaks between 1˜6 degrees 2θ and multiple diffraction peaksindicative of zeolite Y at 2θ values between 5˜50 degrees (FIG. 32). Thenitrogen adsorption-desorption isotherms (FIG. 33) were of type IV andshow steep hysteresis of type H1 at relative pressure between 0.2˜0.4.This isotherm is typical of mesoporous materials that exhibits capillarycondensation and evaporation with a narrow pore size distribution.Moreover, the calcined composite exhibited a single ²⁷Al MAS NMRchemical shift at about 62 ppm which is comparable to the shift of steamstable Y zeolites (FIG. 34). In other words, the aluminosilicate speciesin the composite exhibit an ²⁷Al NMR pattern consistent with thepresence of faujasitic subunits, as reported in the literature fortypical zeolite Y seeds (Y. Liu, W. Zhang, and T. J. Pinnavaia, J. Am.Chem. Soc. 122, 8791 (2000)). The single ²⁷Al NMR chemical shift at ˜62ppm indicates that the framework of mesostructure composited offaujasite seeds which is different from a conventional Al-MCM-41mesostructured (chemical shift at ˜55 ppm) or a mechanical mix of MCM-41and zeolite Y.

EXAMPLE 32

[0290] This example demonstrates the preparation of a mesostructuredMSU-S/microstructured ZSM-5 zeolite composite composition made from amixture of ZSM-5 seeds and nanosized ZSM-5 zeolite crystals.

[0291] To prepare the mixture of MFI zeolite seeds and nanosized ZSM-5zeolite crystals, 0.17 g of aluminum sec-butoxide was added withstirring to 7.22 ml of 1.0 M tetrapropylammonium hydroxide and thentetraethylorthosilicate (6.83 g) was added to form a clear solution. A70-ml portion of water was added to the stirred solution, and thesolution was allowed to age to 100° C. overnight (16 hr) under staticconditions to form a cloudy mixture of ZSM-5 zeolite seeds and nanosizedZSM-5 crystals. A 2.45-g portion of cetyltrimethylammonium bromide thenwas added under vigorous stirring for 30 minutes, and the resultingmixture was allowed to age at 100° C. under static conditions overnight(16 h). The pH of the reaction mixture was lowered to a value of 9.0 bythe addition of 1.0 M sulfuric acid and the reaction mixture was agedagain overnight at 100° C. under static conditions. Themesoporous/microporous composite precipitate was filtered, washed, driedin air and then calcined at 550° C. to remove the surfactant.

[0292] The X-ray powder diffraction pattern of the calcined productexhibited diffraction lines at 2θ values between 1˜5 degrees consistentwith a mesostructure and diffraction lines at 2θ values between 5˜50degrees consistent with a ZSM-5 zeolite phase (FIG. 35). The steamstability of the mesoporous/microporous composite was tested at 800° C.for 2 h in 20% steam. As shown by the nitrogen adsorption/desorptionisotherms in FIG. 36, before and after steaming in 20% steam at 800° C.for 2 h, the composite material still retained 80% of its initialsurface area and pore volume.

EXAMPLE 33

[0293] The purpose of this example is to illustrate that zeolite seedsuseful for the preparation of a steam stable MSU-S mesostructure or asteam stable composite of a MSU-S mesostructure and a microstructuredcrystalline zeolite be prepared from a crystalline zeolite.

[0294] In order to prepare a composite mixture of reconstructuredzeolite seeds and nanosized zeolite Beta crystals, 2 g Zeolite Beta(Si/Al=37.5, Zeolyst Co.) was added with stirring to 50 mL 0.19 mol NaOHsolution. The mixture was heated under static conditions at 100° C. for2.5 h to form the reconstituted seeds. A 2.45 g portion ofcetyltrimethylammonium bromide in 25 ml H₂O then was added undervigorous stirring for 30 minutes, and the resulting mixture was allowedto age at 100° C. under static conditions overnight (16 h) to form amixture of zeolite beta and zeolite beta seeds. The pH of the reactionmixture was lowered to a value of 9.0 by the addition of 0.156 gsulfuric acid and the reaction mixture was aged again overnight at 100°C. under static conditions to form a mesostructure from the remainingzeolite beta seeds. The mesoporous/microporous composite precipitate wasfiltered, washed, dried in air and then calcined at 55° C. to remove thesurfactant.

[0295] The X-ray powder diffraction pattern of the calcined productexhibited diffraction lines 2θ values between 1˜5 degrees consistentwith a hexagonal mesostructure and diffraction lines at 2θ valuesbetween 5˜50 degrees consistent with zeolite Beta (FIG. 37). The steamstability of this material was tested at 800° C. in 20% steam. As shownin FIGS. 37, 38 and 38A, after steaming at 800° C., themesoporous/microporous composite material still retained 78% of itsinitial surface area and 65% of its initial pore volume.

EXAMPLE 34

[0296] The purpose of this example is to illustrate that zeolite seedsuseful for the preparation of a steam stable MSU-S mesostructure or asteam stable composite of a MSU-S mesostructure and a microstructuredcrystalline zeolite be prepared from kaolin clay as a precursor.

[0297] In order to prepare a mixture of nanosized faujasite zeolite andnanosized faujasite seeds from kaolinite, kaolinite was first calcinedat 650° C. for 7 h to convert to metakaolin. The, 0.6 g metakaolin wasadded to 5.2 g sodium silicate solution (27% SiO₂, 14% NaOH) with 0.411g NaOH, and 5 ml H₂O under stirring condition. The mixture was stirredat ambient temperature for 24 h and heated at 90° C. for 16 h. Theresultant mixture was comprised of nanosized faujasitic zeolite Ycrystals and nanosized faujasite seeds.

[0298] The above mixture was diluted with 75 ml water. To the dilutedmixture, was added sequentially 0.142 g H₂SO₄ and 2.45 g CTAB understirring at room temperature for 30 minutes. The resultant mixture wasfurther acidified with 0.781H₂SO₄ and aged at 100° C. for 24 h. Then themixture was acidified with 0.156 g H₂SO₄ and aged at 100° C. for 24 hagain. The final solid was recovered by filtration, washed andair-dried. The as-made mesostructure was exchanged with 0.1 M NH₄NO₃solution, air dried and calcined at 550° C. for 4 h.

[0299] The calcined hexagonal mesostructured/microstructured compositeexhibited diffraction lines at 2θ values between 1˜6 degreescharacteristic of a hexagonal mesostructure and multiple diffractionlines at 2θ values between 5˜50 degrees indicative of zeolite Y crystals(FIG. 39). The isotherms (FIGS. 40 and 40A) are of type IV and showsteep hystereses of type H1 at relative pressure between 0.2˜0.4, whichis typical for mesoporous materials that exhibit capillary condensationand evaporation with narrow pore size distribution. Moreover, thecalcined mesostructures exhibited a single ²⁷Al MAS NMR chemical shiftat about ˜62 ppm which is comparable to the shift for steam stable Y.The steam stability of the mesoporous/microporous composite was testedat 800° C. for 2 h in 20% steam. As shown in FIG. 44, after exposure to20% steam at 800° C. for 2 h, the composition retained 75% of itsinitial surface area and pore volume.

EXAMPLE 35

[0300] The purpose of this example is to illustrate that hydrothermallystable a mesostructured/microstructured aluminosilicate composite can beprepared from metakaolin, sodium silicate and sodium aluminate.

[0301] To prepare the faujasite seeds, 0.6 g metakaolin, prepared asdescribed in Example 4, was added to 5.2 g sodium silicate solution (27%SiO₂, 14% NaOH) with 0.411 g NaOH, 0.05 g NaAlO₂ and 5 ml H₂O understirring condition. The mixture was stirred at ambient temperature for24 h and heated at 80° C. for 16 h. The resultant mixture composed purenanosized faujasite seeds, but no crystalline zeolite phase as judged bythe absence of characteristic XRD lines in the diffraction patternbetween 10-50 degrees 2θ.

[0302] The above mixture was diluted with 75 ml water. To the dilutedmixture, was added sequentially 0.142 g H₂SO₄ and 2.45 g CTAB understirring at room temperature for 30 minutes. The resultant mixture wasfurther acidified with 0.781 g H₂SO₄ and aged at 100° C. for 48 h. Thefinal solid was recovered by filtration washing and air dried. Theas-made mesostructure was exchanged with 0.1 M NH₄NO₃ solution, airdried and calcined at 550° C. for 4 h. The calcined hexagonal micro/mesomesostructured/microstructured product exhibited hexagonal mesostructurediffraction lines at 2θ values between 1˜6 degrees and nanosized zeoliteY crystals at 2θ values between 5-50 degrees (FIG. 41). The isotherms(FIGS. 42 and 42A) are of type IV and show steep hystereses of type H1at relative pressure between 0.2˜0.4, which is typical for mesoporousmaterials that exhibit capillary condensation and evaporation withnarrow pore size distribution. Moreover, the calcined mesostructuresexhibited a single ²⁷Al MAS NMR chemical shift at about ˜62 ppm which iscomparable to the shift of steam stable Y. The steam stability of themesoporous/microporous composite was tested at 800° C. for 2 h in 20%steam. As shown in FIG. 46, after exposure to 20% steam at 800° C. for 2h, the composition retained 78% of its initial surface area and 85% ofits pore volume.

EXAMPLE 36

[0303] The purpose of this example is to illustrate that ahydrothermally stable hexagonal mesostructured Aluminosilicate MSU-S canbe prepared from metakaolin, sodium silicate and sodium aluminate.

[0304] To prepare the faujasite seeds, 0.6 g metakaolin, prepared asdescribed in Example 4, was added to 5.2 g sodium silicate solution (27%SiO₂, 14% NaOH) with 0.411 g NaOH, 0.05 g NaAlO₂ and 5 ml H₂O understirring conditions. The mixture was stirred at ambient temperature for24 h and heated at 80° C. for 16 h. The resultant mixture containednanosized faujasite seeds, but no crystalline zeolite phase as judged bythe absence of characteristic XRD lines in the diffraction patternbetween 10-50 degrees 2θ.

[0305] The above mixture was diluted with 75 ml water. To the dilutedmixture, was added sequentially 0.142 g H₂SO₄ and 2.45 g CTAB understirring at room temperature for 30 minutes. The resultant mixture wasacidified with 0.781 g H₂SO₄ and aged at 100° C. for 18 h, then furtheracidified with 0.156 g H₂SO₄ and aged at 100° C. for another 18 h. Thefinal solid was recovered by filtration washing and air dried. Theas-made mesostructure was exchanged with 0.1 M NH₄NO₃ solution, airdried and calcined at 550° C. for 4 h.

[0306] The calcined product exhibited diffraction lines characteristicof a hexagonal mesostructure at 2θ values between 1˜6 degrees and nodiffraction lines at 2θ values between 5˜50 degrees (FIG. 43), verifyingthe absence of a crystalline zeolite phases. The isotherms (FIGS. 44 and44A) are of type IV and show steep hysteresis of type H1 at relativepressure between 0.2˜0.4, which is typical for mesoporous materials thatexhibit capillary condensation and evaporation with narrow pore sizedistribution. Moreover, the calcined mesostructures exhibited a single²⁷Al MAS NMR chemical shift at about ˜62 ppm which is comparable to theshift observed for steam stable zeolite Y.

EXAMPLE 37

[0307] The purpose of this example is to illustrate that zeolitefragments useful for the preparation of a steam stable MSU-Smesostructure from a crystalline zeolite.

[0308] In order to reconstitute the zeolite into zeolite fragments, 2 gof ultrastable zeolite Y (Si/Al=39, Zeolyst Co.) was added with stirringto 30 mL 0.19 molar NaOH solution and stirred for 30 min. To therestructured zeolite fragments solution, a 2.45 g portion ofcetyltrimethylammonium bromide in 25 ml H₂O then was added undervigorous stirring for 30 minutes, and the resulting mixture was allowedto age at 100° C. under static conditions for 16 h. Then the pH of thereaction mixture was lowered to a value of 9.0 by the addition of 0.156g sulfuric acid and the reaction mixture was aged again overnight at100° C. under static conditions. The precipitate was filtered, washed,dried in air and then calcined at 550° C. to remove the surfactant.

[0309] The x-ray powder diffraction pattern of the calcined productexhibited diffraction lines at 2θ values between 1˜5 degrees consistentwith a hexagonal mesostructure and no diffraction lines at 2θ valuesbetween 5˜50 (FIG. 45).

[0310] The isotherms (FIG. 46) are of type IV and show steep hysteresesof type H1 at relative pressure between 0.2˜0.4, which is typical formesoporous materials that exhibit capillary condensation and evaporationwith narrow pore size distribution.

EXAMPLE 38

[0311] The purpose of this example was to demonstrate that fragmentscontaining zeolitic subunits derived from the ultrasonic degradation ofthe delaminated ITQ-2 layers of MCM-22 zeolite, were useful for thepreparation of a steam stable aluminosilicate mesostructure, which wedenote MSU-S/ITQ.

[0312] In order to prepare nanosized fragments of zeolite MCM-22,delaminated ITQ-2 layers were prepared from the precursor of zeoliteMCM-22, denoted MCM-22 (P) (Corma, A., Nature 353 (1998)). A 0.23-gquantity of NaAlO₂ and a 0.81-g amount of NaOH were dissolved in 103.5 gH₂O under stirring at ambient temperature. Then 6.35 g hexamethylenimine(HMI) and 7.86 g fumed silica were added under stirring at ambienttemperature for 30 min. The mixture then was transferred to an autoclaveand aged at 190° C. for 11 days under stirring. The resulting MCM-22(P)solid was washed with H₂O until pH <8, centrifuged, and dried at roomtemperature. Then 1.35 g of the dried MCM-22(P) was added to 5.4 g H₂Oto form a slurry. Then 7.6 g cetyltrimethylammonium bromide in 26 ml H₂Owas added under stirring. To the mixture was added 9.45 g of 35%tetraethylammonium hydroxide. After refluxing at 80° C. for 16 h, 25 mlH₂O was added and the pH of the mixture was adjusted to ca. 12.5 withtetraethyl ammonium hydroxide. The mixture was cooled in a cold waterbath and then subjected to ultrasonication by a ultrasonic horn for 1hour. A few drops of strong HCl acid was added to adjust the suspensionto pH=2. The mixture was centrifuged to obtain a solid containing thetransformed ITQ-2 layers containing zeolitic subunits. The transformedITQ-2 fragments were washed with acetone:water=1:1 (v/v) solution andthen air dried.

[0313] To assemble the transformed nanosized ITQ-2 fragments containingzeolitic subunits into a mesoporous material, 10 ml H₂O, 1.1 g CTAB and1.22 g 20% tetramethylammonium hydroxide was added consecutively andtransferred to an autoclave. The autoclave was heated at 150° C. for 40h. The final solid was recovered by filtration, washed and air-dried.The surfactant was removed by calcination at 550° C. for 4 hours and theproduct was denoted MSU-S/ITQ-2.

[0314] The X-ray powder diffraction patterns of the calcined productbefore and after steaming at 800° C. for 2 hours are shown in FIG. 47.Clearly, MSU-S/ITQ was still stable after steaming at 800° C. Also, inthe wide angle scattering range, weak ITQ-2 peaks were observed, whichconfirms that MSU-S/ITQ was successfully assembled by using nanosizedaluminosilicate particles derived from delaminated ITQ-2 layers.

[0315] The isotherms (FIG. 48) are of type IV and show steep hysteresesof type H1 at relative pressure between 0.2-0.4, which is typical formesoporous materials that exhibit capillary condensation and evaporationwith a narrow pore size distribution. The steam stability of themesoporous/microporous composite was tested at 800° C. for 2 hours in20% steam. As shown in FIG. 48, before and after steaming in 20% steamat 800° C. for 2 hours, the material still retained 83% of its initialsurface area and 85% of its pore volume.

[0316] The TEM image of MSU-S/ITQ was shown in FIG. 49 which furtherconfirmed the mesophase of MSU-S/ITQ.

EXAMPLE 39

[0317] The purpose of this example was to illustrate the preparation ofa hydrothermally stable wormhole mesostructure using zeolite beta seedsand a small, non-surfactant organic molecule as a porogen, namelytriethanol amine, in place of a surfactant. The product was denotedMSU-S/TEA.

[0318] In order to make zeolite Beta seeds containing 2 mol % Al, 0.11 gof aluminum sec-butoxide was added with stirring to 3.3 g of 35%tetraethylammonium hydroxide and then 4.4 g of tetraethylorthosilicateand 4 ml H₂O were added to form a clear solution under vigorous stirringovernight at ambient temperature. Then the clear solution was aged at100° C. for 3-10 h. 3.2 g triethanolamine was added under stirring atambient temperature for 24 h and heated at 80-100° C. under stirring for2-4 hours to vaporize ethanol and H₂O. The dry gel was aged at 100° C.for 48 hours and final products were obtained by calcination at 650° C.for 10 hours with the ramp rate at 1° C./min.

[0319] The isotherms (FIG. 50) were of type IV and showed a hysteresesof type H1 at relative pressure between 0.2˜0.4, which was typical formesoporous materials that exhibit capillary condensation. Furtherevidence for the presence of uniform mesoporous of MSU-S/TEA wasprovided by TEM images (FIG. 51). The steam stability of this materialwas tested at 800° C. in 20% steam for 2 hours. As shown in FIG. 50,after steaming at 800° C., the material still retained 81% of itsinitial surface area and 89% of its initial pore volume.

[0320] It is intended that the foregoing description be onlyillustrative of the present invention and that the present invention belimited only by the hereinafter appended claims.

We claim:
 1. A porous structured aluminosilicate composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining pores and having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, and wherein the composition retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours.
 2. A porous structured aluminosilicate composition which comprises: a framework of linked SiO₄ and AlO₄ units, the framework defining pores and having a Si to Al molar ratio of about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak between 2 and 100 nm, and wherein the composition retains at least 75% of an initial framework pore volume after exposure to 20 volume percent steam at 600° C. for four hours.
 3. The composition of claim 1 or 2 assembled from preformed zeolite seeds or zeolite fragments.
 4. The composition of claim 1 or 2 having a BET surface area of between about 200 and 1400 m² per gram, an average pore size between about 1 and 100 nm and a pore volume of between about 0.1 and 3.5 cm³ per gram.
 5. The composition of claim 3 wherein the zeolite seeds are formed using a structure director selected from the group consisting of organic onium ions, alkali metal ions and mixtures thereof.
 6. A porous structured aluminosilicate composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining pores having an organic surfactant in the pores and having a Si to Al molar ratio of between 1000 to 1 and 1 to 1 and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2 and 100 nm and wherein the composition is derived from a porogen and preformed zeolite seeds or zeolite fragments.
 7. The composition of claim 6 wherein the porogen is an organic surfactant is selected from the group consisting of an organic onium ion surfactant and a non-ionic surfactant.
 8. The composition of claim 7 wherein the surfactant is a non-ionic surfactant selected from the group consisting of a non-ionic polyethylene oxide surfactant and a non-ionic amine surfactant.
 9. The composition of claim 6 wherein the zeolite seeds are formed using a structure director selected from the group consisting of organic onium ions, alkali metal ions and mixtures thereof.
 10. The composition of claim 1, 2 or 3 containing between about 0.1 and 50% by weight carbon in the framework pores.
 11. The composition of claims 1 and 2 with an infrared absorption band between 500 and 600 cm⁻¹.
 12. The composition of claim 6 wherein the porogen is an organic surfactant which contains a co-surfactant selected from the group consisting of alkyl alcohol, alkyl amine, aromatic hydrocarbon and mixtures thereof containing between about 2 and 36 carbon atoms in the alkyl and 6 to 36 carbon atoms in the aromatic hydrocarbon.
 13. A process for forming a porous aluminosilicate composition which comprises: (a) providing zeolite seeds or zeolite fragments in a form selected from the group consisting of an aqueous solution, gel, suspension wetted powder and mixtures thereof; (b) mixing in a mixture the zeolite seeds or zeolite fragments in an aqueous medium with an organic porogen; (c) aging the mixture of step (b) at a temperature between 25° and 200° C. to obtain a precipitate of the composition; and (d) separating the composition from the mixture of step (c).
 14. The process of claim 13 wherein the porogen is a surfactant.
 15. The process of claim 14 wherein the organic surfactant is selected from the group consisting of onium ion surfactants and non-ionic surfactants.
 16. The process of claim 13 wherein the porogen is an organic surfactant which contains a co-surfactant selected from the group consisting of alkyl alcohol, alkylamine, aromatic hydrocarbon and mixtures thereof containing between about 2 and 36 carbon atoms in the alkyl and 6 to 36 carbon atoms in the aromatic hydrocarbon.
 17. The process of claim 13 or 14 wherein the zeolite seeds are formed using a structure director selected from the group consisting of organic onium ions, alkali metal ions and mixtures thereof.
 18. The process of claim 13 or 14 wherein in addition the composition is calcined.
 19. The process of claim 13 or 14 wherein in addition the composition is calcined at above about 400° C.
 20. A structured aluminosilicate porous composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining mesopores, having a porogen in the pores of the composition, having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2.0 and 100 nm, and which when calcined retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours.
 21. The composition of claim 20 wherein the porogen is a surfactant is selected from the group consisting of: (a) an ammonium or phosphonium ion of the formula R₁R₂R₃R₄Q⁺, wherein Q is nitrogen or phosphorous, and wherein at least one of the R moieties is selected from the group consisting of aryl, alkyl of between about 6 to 36 carbon atoms and combinations thereof, remaining of the R moieties are selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, and (b) a non-ionic block surfactant containing polyethylene oxide units in a hydrophilic block and polypropylene oxide, polybutylene oxide, alkyl, or aryl units in a hydrophobic block, and nonionic amine surfactants containing 6 to 36 carbon atoms.
 22. The composition of claim 20 wherein the porogen is a surfactant and a co-surfactant and the co-surfactant is selected from the group alkyl amine, alkyl alcohol, aromatic hydrocarbon and mixtures thereof, wherein the number of carbon atoms in the co-surfactant is between 2 and
 36. 23. The composition of any one of claim 1, 2, 6 or 20 wherein the framework has a structure which is hexagonal, cubic, lamellar, wormhole or cellular foam.
 24. The composition of claim 6 or 20 wherein the porogen is removed by calcination, by ion exchange, or by a combination of ion exchange and calcination.
 25. A porous aluminosilicate composition which comprises: a framework of tetrahedral linked SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2.0 and 100 nm, wherein a BET surface area is between 200 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein 10 a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours.
 26. The composition of claim 25 wherein the framework has a structure which is hexagonal, cubic, lamellar, wormhole, or cellular foam.
 27. A hybrid porous aluminosilicate-carbon composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1 and between 0.01 and 50 wt % carbon embedded in the mesopores, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2.0 and 100 nm, wherein a BET surface area is between 100 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours.
 28. The composition of claim 27 wherein the framework has a structure which is hexagonal, cubic, lamellar, wormhole, or cellular foam.
 29. A composition prepared by treating the composition of claim 20 before calcining with an ammonium salt solution at a temperature between about 0° and 200° C. for a period of up to 24 hours and repeating the treatment up to ten times to introduce ammonium ions into the composition, collecting and drying the resulting composition, and then calcining the resulting composition at a temperature between about 40° and 900° C. to remove the organic porogen and to convert a fraction of the surfactant or other organic porogen to carbon embedded in the mesopores.
 30. A process for forming a porous aluminosilicate composition which comprises: (a) reacting a sodium silicate solution at basic pH with a sodium aluminate solution at an aluminum to silicon ratio between about 1000 to 1 and 1 to 1 and aging the mixture at 25 to 200° C. for periods of up to 48 hours to form zeolite seeds; (b) mixing the resultant mixture with an organic porogen; (c) reducing a pH of the mixture obtained from (b) with a protonic acid to obtain a mixture with an OH⁻/(Si+Al) ratio in the range of 0.10 to 10; (d) aging the mixture from step (c) at a temperature between 20 and 200° C. to obtain a precipitate of the composition; and (e) separating the composition from mixture of step (d).
 31. The process of claim 30 wherein the sodium silicate is prepared by reacting sodium hydroxide with a silicon source selected from the group consisting of a colloidal silica, a fumed silica, a silica gel, a silicon alkoxide and mixtures thereof.
 32. The process of claim 30 wherein the sodium aluminate is prepared by reacting sodium hydroxide with an aluminum source selected from the group consisting of a soluble aluminum salt, a cationic aluminum oligomers, an aluminum hydroxide, an aluminum oxide, an aluminum alkoxide and mixtures thereof.
 33. The process of claim 30 wherein the organic porogen is a surfactant selected from the group consisting of: (a) a alkyl quaternary ammonium surfactant with a hydrophobic segment which contains between 8 to 36 carbon atoms, (b) a non-ionic surfactant containing a polyethylene oxide block as a hydrophilic segment, and (c) a non-ionic amine surfactant.
 34. The process of claim 30 wherein the composition has a ²⁷Al-NMR resonance line exhibiting a chemical shift in the range of 57 to 65 ppm relative to an external reference of 1.0 M aluminum nitrate.
 35. A process for forming a porous aluminosilicate composition which comprises: (a) providing zeolite seeds or zeolite fragments in a form selected from the group consisting of an aqueous solution, gel, suspension, wet powder, or combination thereof; (b) reacting the zeolite seeds in the aqueous medium with an organic porogen wherein the solution has an OH⁻/(Si+Al) ratio in the range of 0.10 to 10; (c) aging the mixture from step (b) at a temperature between 20 and 200° C. to obtain a precipitate of the composition; and (d) separating the composition from the mixture of step (c).
 36. A catalyst useful for a fluidized bed catalytic cracking (FCC) or hydrocracking of an organic molecule which comprises: (a) a porous aluminosilicate composition which comprises a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, wherein a BET surface area is between 200 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours; and (b) a binder for the aluminosilicate composition.
 37. A catalyst useful for fluidized bed catalytic cracking (FCC) or hydrocracking of an organic molecule which comprises: (a) a porous aluminosilicate-carbon composition which comprises a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1 and between 0.01 and 50 wt % carbon embedded in the mesopores, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2.0 and 100 nm, wherein a BET surface area is between 100 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram, wherein the carbon content is between 0.01 and 50% by weight, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours; and (b) a binder for the aluminosilicate-carbon composition.
 38. A process for catalytic reaction of an organic molecule into lower molecular weight components, which comprises: (a) providing in a reactor a catalytic cracking catalyst which comprises: a porous aluminosilicate composition which comprises a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, wherein a BET surface area is between 200 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram; and a binder for the aluminosilicate composition, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours; and (b) introducing the organic molecule onto the catalyst at temperatures and pressures which cause the reaction of the organic molecule.
 39. A process for reaction of an organic molecule into lower molecular weight components, which comprises: (a) providing in a reactor a catalytic cracking catalyst which comprises: a porous aluminosilicate-carbon composition which comprises: a framework of tetrahedral linked SiO₄ and AlO₄ units, the framework defining mesopores having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1 and between 0.01 and 50 wt % carbon embedded in the mesopores, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2.0 and 100 nm, wherein a BET surface area is between 100 and 1400 m² per gram, wherein an average pore size of the framework is between about 1.0 and 100 nm, and wherein a pore volume of the framework is between about 0.1 and 3.5 cm³ per gram; and a binder for the aluminosilicate-carbon composition, and which retains at least 50% of an initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours; and (b) introducing the organic molecule onto the catalyst at temperatures and pressures which cause the reaction of the organic molecule into lower molecular weight components.
 40. A catalyst useful for a fluidized bed catalytic cracking (FCC) or hydrocracking of an organic molecule which comprises: (a) a porous structured aluminosilicate composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining pores and having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, and wherein the composition retains at least 50% of the initial framework pore volume after exposure to 20 volume % steam at 800° C. for two hours; and (b) a binder for the aluminosilicate composition.
 41. A process for reaction of an organic molecule into lower molecular weight components which comprises: (a) providing a porous structured aluminosilicate composition which comprises: a framework of linked tetrahedral SiO₄ and AlO₄ units, the framework defining pores and having an Si to Al molar ratio of between about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 1 and 100 nm, and wherein the composition retains 50% of the initial framework pore volume upon exposure to 20 volume percent steam at 800° C. for two hours; and (b) introducing the organic molecule onto the catalyst at temperatures and pressures which cause the reaction of the organic molecule to produce the lower molecular weight components.
 42. In a catalyzed organic reaction process, the improvement which comprises: conducting the reaction with a catalyst which is selected from the group consisting of a porous structured aluminosilicate, gallosilicate, titanosilicate and mixtures thereof which catalyst comprises: a framework of linked tetrahedral SiO₄ and AlO₄, GaO₄ or TiO₄ units, the framework defining pores and having an Si to combined Ga, Ti and Al molar ratio of between about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 2 and 100 nm, and wherein the composition retains at least 50% of initial framework pore volume after exposure to 20 volume % steam at 600° C. for four hours.
 43. A porous structured silicate composition which comprises: a framework of linked tetrahedral SiO₄ and units selected from the group consisting of AlO₄ units, GaO₄ units, TiO₄ units and mixed units, the framework defining pores and having an Si to combined Ga, Ti and Al molar ratio of between about 1000 to 1 and 1 to 1, and having at least one X-ray diffraction peak corresponding to a basal spacing between about 1 and 100 nm, and wherein the composition retains at least 50% of the initial framework pore volume after exposure to 20 volume percent steam at 600° C. for four hours.
 44. The composition of claim 43 assembled from preformed nanoclustered seed precursors.
 45. The composition of claim 43 or 44 having an X-ray diffraction peak corresponding to a basal spacing between about 2 and 100 nm, a BET surface area of between about 200 and 1400 m² per gram, an average pore size between about 1 and 100 nm and a pore volume of between about 0.1 and 3.5 cm³ per gram.
 46. The composition of claim 44 wherein the seed precursors are formed using a structure director selected from the group consisting of organic onium ions, alkali metal ions and mixtures thereof.
 47. The composition of claims 1 and 2 with a ²⁷Al NMR chemical shift between about 57 and 65 ppm relative to an external reference of 1.0 M aluminum nitrate.
 48. The composition of claim 1 which contains zeolite crystals.
 49. The composition of claim 2 which contains zeolite crystals.
 50. The composition of claim 6 which contains zeolite crystals.
 51. The composition of claim 6 wherein the zeolite fragments are derived from zeolite crystals by digesting with a base.
 52. The composition of claim 6 wherein the zeolite fragments are derived from a naturally occurring crystalline zeolite.
 53. The process of claim 13 wherein seeds are aged to form zeolite crystals in step (a) prior to addition of the organic porogen.
 54. The process of claim 13 wherein the zeolite fragments in step (a) are produced by digesting zeolite crystals with a base.
 55. The process of claim 13 wherein the zeolite fragments are derived from naturally occurring zeolite crystals.
 56. The composition of claim 27 which contains zeolite crystals.
 57. The catalyst of claim 36 which contains zeolite crystals.
 58. The catalyst of claim 37 which contains zeolite crystals.
 59. The process of claim 38 wherein the catalyst contains zeolite seeds.
 60. The process of claim 39 wherein the catalyst contains zeolite seeds.
 61. The catalyst of claim 40 which contains zeolite crystals.
 62. The process of claim 41 wherein the catalyst contains zeolite seeds.
 63. The reaction of claim 42 where the catalyst contains zeolite seeds or zeolite fragments.
 64. The composition of claim 43 wherein the catalyst contains zeolite seeds or zeolite fragments.
 65. A process for forming a porous aluminosilicate composition which comprises: (a) providing zeolite fragments prepared by disrupting the structure of a crystalline aluminosilicate zeolite in a form selected from the group consisting of an aqueous solution, gel, suspension, wetted powder, and mixtures thereof; (b) mixing in a mixture the zeolite fragments in an aqueous medium with an organic porogen; (c) aging the mixture of step (b) at a temperature between 250 and 200° C. to obtain a precipitate of the composition; and (d) separating the composition from the mixture of step (c).
 66. The process of claim 65 wherein the fragments are formed by disrupting the structure of a synthetic or naturally occurring zeolite.
 67. The process of claim 65 or 66 wherein the organic porogen is an organic surfactant selected from the group consisting of onium ion surfactants and non-ionic surfactants.
 68. The process of claim 65 wherein the porogen is an organic surfactant which contains a co-surfactant selected from the group consisting of alkyl alcohol, alkylamine, aromatic hydrocarbon and mixtures thereof containing between about 2 and 36 carbon atoms in the alkyl and 6 to 36 carbon atoms in the aromatic hydrocarbon.
 69. The process of claim 65 wherein the zeolite fragments are formed by disrupting the structure of a zeolite through treatment with a base or by subjecting the zeolite to ultrasound, grinding, milling or a combination thereof.
 70. The process of claim 65 or 66 wherein in addition the composition is calcined.
 71. The process of claim 65 or 66 wherein in addition the composition is calcined at above about 400° C.
 72. The process of claim 20 wherein the porogen is a non-surfactant.
 73. The process of claim 20 wherein the porogen is triethanolamine.
 74. A product prepared by the process of claim
 65. 75. The composition of claim 1 having at least one x-ray diffraction peak corresponding to a basal spacing of about 2 and 100 nm.
 76. The composition of claim 1 having no x-ray diffraction peaks.
 77. The process of claim 13 wherein the zeolite fragment is formed from a crystalline zeolite selected from a group consisting of zeolite Y, zeolite X, zeolite ZSM-5, zeolite ZMS-11, zeolite Beta, and zeolite MCM-22.
 78. The process of claim 13 wherein the zeolite fragment is formed from MCM-22(P), the precursor of zeolite MCM-22.
 79. A carbon composition obtained from the composition of any one of claim 27, 28 or 29, wherein the aluminosilicate component is removed by dissolving in aqueous base or hydrofluoric acid.
 80. The composition of claim 6 wherein the porogen is selected from the group consisting of an amine, ethoxylated amine or alkoxylated amine.
 81. The process of claim 13 wherein the zeolite fragment is formed from a crystalline zeolite or a crystalline zeolite precursor.
 82. The composition of claim 6 wherein the zeolite seeds or fragments are derived from a crystalline aluminosilicate. The composition of claim 82 wherein the crystalline aluminosilicate is a clay. 